WO2004055082A2 - Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase - Google Patents

Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase Download PDF

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Publication number
WO2004055082A2
WO2004055082A2 PCT/FR2003/003714 FR0303714W WO2004055082A2 WO 2004055082 A2 WO2004055082 A2 WO 2004055082A2 FR 0303714 W FR0303714 W FR 0303714W WO 2004055082 A2 WO2004055082 A2 WO 2004055082A2
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WO
WIPO (PCT)
Prior art keywords
composition according
weight
chosen
silicone
group
Prior art date
Application number
PCT/FR2003/003714
Other languages
French (fr)
Other versions
WO2004055082A3 (en
Inventor
Xavier Blin
Nathalie Jager Lezer
Bertrand Lion
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0215737A external-priority patent/FR2848558B1/en
Priority claimed from FR0215738A external-priority patent/FR2848559B1/en
Priority claimed from FR0215739A external-priority patent/FR2848560B1/en
Priority to JP2004559837A priority Critical patent/JP4167229B2/en
Priority to ES03813190.0T priority patent/ES2627551T3/en
Priority to US10/538,783 priority patent/US7794695B2/en
Priority to AU2003300602A priority patent/AU2003300602A1/en
Priority to EP03813190.0A priority patent/EP1572137B1/en
Application filed by L'oreal filed Critical L'oreal
Priority to FR0450540A priority patent/FR2863493B1/en
Publication of WO2004055082A2 publication Critical patent/WO2004055082A2/en
Publication of WO2004055082A3 publication Critical patent/WO2004055082A3/en
Priority to PCT/IB2004/004127 priority patent/WO2005058274A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91Graft copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06Lipsticks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/08Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/10Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/04Preparations for care of the skin for chemically tanning the skin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04Polymers provided for in subclasses C08C or C08F
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/068Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • Non-transfer cosmetic composition comprising a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase
  • the subject of the present invention is a cosmetic composition
  • a cosmetic composition comprising a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase, intended to be applied to keratin materials of human beings, such as the skin, the lips, the nails. , keratin fibers such as eyelashes, eyebrows, hair.
  • composition according to the invention may be a makeup composition or a care composition for keratin materials, in particular the skin, lips and keratin fibers, in particular eyelashes, and preferably a makeup composition.
  • the makeup composition can be a lip makeup product (lipstick), a foundation, an eyeshadow, a blush, a concealer product, an eyeliner, a body makeup product, a mascara, nail polish, hair makeup product.
  • lip makeup product lipstick
  • a foundation an eyeshadow, a blush, a concealer product, an eyeliner
  • a body makeup product a mascara, nail polish, hair makeup product.
  • the care composition may be a care product for the skin of the body and the face, in particular a sun care product, a product for coloring the skin (such as a self-tanner).
  • the composition can also be a hair product, in particular for maintaining the hairstyle or shaping the hair, or even an eyelash care product.
  • Lipstick and foundation compositions are commonly used to provide an aesthetic color to the lips or to the skin, in particular to the face.
  • These makeup products generally contain fatty phases such as waxes and oils, pigments and / or fillers and optionally additives such as cosmetic or dermatological active agents.
  • compositions when applied to the skin, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact. and in particular a glass, a cup, a cigarette, a garment or the skin. It follows a mediocre persistence of the applied film, requiring to regularly renew the application of the foundation or lipstick composition. Furthermore, the appearance of these unacceptable traces, in particular on shirt collars, may exclude certain women from the use of this type of makeup.
  • Products are also known in the form of two separate compositions to be applied one on the other on the lips to obtain makeup without transfer.
  • LIP FINITY by MAX FACTOR is a two-layer product, the base composition of which (called base coat) contains a silicone resin and volatile oils, and the surface composition (so-called top coat) contains a sucrose ester (as described in application WO 97/17057) to improve the comfort of the non-transfer makeup product.
  • base coat contains a silicone resin and volatile oils
  • top coat contains a sucrose ester (as described in application WO 97/17057) to improve the comfort of the non-transfer makeup product.
  • the application of two makeup compositions can be prohibitive for some users.
  • the present invention aims to provide a new way of formulating a cosmetic composition, in particular make-up, making it possible to obtain a deposit having good non-transfer properties, in particular without using a high rate of volatile oils, and this , without requiring the application of two separate compositions to obtain the result.
  • the invention also aims to provide a cosmetic composition, in particular make-up, making it possible to obtain a comfortable deposit on the skin, the lips or the keratin fibers.
  • the inventors have discovered that it is possible to obtain such a composition by using a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase as described below.
  • the composition makes it possible to obtain a deposit, in particular a make-up of keratin materials, in particular of the skin, the lips or keratin fibers, having good non-transfer properties.
  • the deposit obtained on the skin or the lips does not cause a feeling of dryness or tightness for the user: the deposit is therefore comfortable.
  • the present invention therefore relates to a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, at least one dispersion of particles, preferably solid, of a non-grafted ethylenic polymer. silicone in a liquid fatty phase as described below, the composition being in particular as defined below.
  • the polymer is such that when it is dispersed in sufficient quantity in the composition, the latter is capable of forming a deposit having a transfer less than or equal to 35% .
  • the composition according to the invention is capable of forming a deposit having a transfer less than or equal to 30%, preferably less than or equal to 25%, preferably less than or equal to 20%, preferably less than or equal to 15% , preferably less than or equal to 10%, preferably less than or equal to 5%.
  • the subject of the invention is also a cosmetic process for making up or for non-therapeutic care of keratin materials, in particular of the skin, lips or keratin fibers, comprising the application to keratin materials, in particular on the skin or lips, of a composition as defined above.
  • the subject of the invention is also the use of a composition as defined above to obtain a non-transfer deposit, in particular make-up, on keratin materials, in particular on the skin, lips or keratin fibers.
  • the subject of the invention is also the use of a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase as defined above, in a cosmetic composition comprising a cosmetically acceptable organic liquid medium, to obtain a deposit. , in particular make-up, non-transfer to keratin materials, in particular to the skin, the lips or the keratin fibers.
  • the transfer of the deposit obtained with the composition according to the invention is determined according to the protocol described below.
  • a support (rectangle of 40 mm X 70 mm and thickness 3 mm) of pre-heated polyethylene foam is preheated on one of the faces having a density of 33 kg / m3 (sold under the name RE40X70EP3 from the company JOINT TECHNIQUE LYONNAIS IND) on a hot plate maintained at a temperature of 40 ° C so that the surface of the support is maintained at a temperature of 33 ° C ⁇ 1 ° C.
  • the composition While leaving the support on the hot plate, the composition is applied to the entire non-adhesive surface of the support, spreading it out using a brush to obtain a deposit of the composition of approximately 15 ⁇ m and then allowed to dry. during 30 minutes.
  • the support After drying, the support is glued by its adhesive side to an anvil with a diameter of 20 mm and provided with a thread.
  • the deposit support assembly is then cut using a punch with a diameter of 18 mm.
  • the anvil is then screwed onto a press (STATIF MANUEL IMADA SV-2 from SOMECO) equipped with a dynanometer (IMADA DPS-20 from SOMECO).
  • a white photocopier paper of 80 g / m2 is placed on the base of the press and then the support / deposition assembly is pressed on the paper at a pressure of 2.5 kg for 30 seconds. After removal of the deposit support assembly, part of the deposit transferred to paper. The color of the deposit transferred to the paper is then measured using a MINOLTA CR300 colorimeter, the color being characterized by the parameters colorimetric L *, a *, b * . The color parameters L * n, a * n, b * o of the color of the bare paper used are determined.
  • the color difference ⁇ E1 is then determined between the color of the transferred deposit relative to the color of the bare paper by the following relationship.
  • a total transfer reference is prepared by applying the composition directly to a paper identical to that used previously, at room temperature (25 ° C), spreading the composition using a brush and to obtain a depositing the composition of about 15 ⁇ m and then allowing it to dry for 30 minutes at room temperature (25 ° C). After drying, the colorimetric parameters L * ', a *', b * 'of the color of the deposit placed on the paper, directly corresponding to the reference color of total transfer, are measured directly. The color parameters L * 'o, a *' o, b * 'o of the color of the bare paper used are determined.
  • the color difference ⁇ E2 is then determined between the reference color of total transfer with respect to the color of the bare paper by the following relation.
  • the measurement is carried out on 4 supports in succession and the transfer value corresponds to the average of the 4 measurements obtained with the 4 supports.
  • composition according to the invention comprises a dispersion of particles of non-silicone grafted ethylenic polymer.
  • ethylenic polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
  • non-silicone graft polymer means a graft polymer mainly containing a carbon macromonomer and optionally containing at most 7% by weight, preferably at most 5% by weight, or even is free of silicone macromonomer.
  • the dispersion of non-silicone grafted ethylenic polymer is in particular free of stabilizing polymer distinct from said grafted polymer, such as those described in EP749747, and the particles of grafted ethylenic polymer are therefore not surface stabilized by such additional stabilizing polymers.
  • the grafted polymer is therefore dispersed in the liquid fatty phase in the absence of additional stabilizer at the surface of the particles.
  • grafted polymer is intended to mean a polymer having a backbone comprising at least one side chain hanging or situated at the end of the chain, and preferably hanging.
  • the non-silicone grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase, and side chains covalently linked to said skeleton and soluble in the liquid fatty phase.
  • the non-silicone grafted ethylenic polymer is in particular a non-crosslinked polymer.
  • the polymer is obtained by polymerization of monomers comprising a single polymerizable group.
  • the non-silicone grafted ethylenic polymer is a film-forming polymer.
  • film-forming polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous film, in particular to the eye and to the touch, and adherent on a support, in particular on materials. keratin.
  • the grafted ethylenic polymer is a grafted acrylic polymer.
  • the non-silicone grafted ethylenic polymer is in particular capable of being obtained by radical polymerization in an organic polymerization medium:
  • At least one ethylenic monomer in particular at least one acrylic monomer and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble skeleton;
  • At least one macromonomer comprising a polymerizable end group to form the side chains, said macromonomer having a weight average molecular weight greater than or equal to 200 and the content of polymerized macromonomer representing from 0.05 to 20% by weight of the polymer .
  • the liquid fatty phase may contain the organic polymerization medium.
  • the liquid organic dispersion medium corresponding to the medium in which the grafted polymer is supplied, may be identical to the polymerization medium.
  • the polymerization medium can be substituted in whole or in part by another liquid organic medium.
  • This other liquid organic medium can be added, after polymerization, to the polymerization medium. The latter is then evaporated in whole or in part.
  • the liquid fatty phase can contain organic liquid compounds other than those present in the dispersion medium. These other compounds are chosen so that the grafted polymer remains in the state of dispersion in the liquid fatty phase.
  • the organic liquid dispersion medium is present in the liquid fatty phase of the composition according to the invention due to the introduction into the composition of the graft polymer dispersion obtained.
  • the liquid fatty phase preferably comprises one or more liquid organic compounds (or oils) as defined below.
  • the liquid fatty phase is a non-aqueous liquid organic phase which is immiscible with water at room temperature (25 ° C).
  • liquid organic compound is understood to mean a non-aqueous compound which is in the liquid state at room temperature (25 ° C.) and which therefore flows from its own weight.
  • silicon compound means a compound containing at least one silicon atom.
  • volatile oil an oil capable of evaporating from the skin or
  • ambient temperature and atmospheric pressure ranging from 10 "3 to 300 mm Hg (0.13 Pa to 40,000 Pa).
  • the volatile oil can be silicone or non-silicone. It can be in particular
  • the volatile oil is advantageously present in a content ranging from 1% to 70% by weight, relative to the total weight of the composition, preferably ranging from 5% to 50% by weight, and preferably ranging from 10% to 35% in weight.
  • the liquid fatty phase may contain a non-volatile oil as described below.
  • the non-volatile oil is advantageously present in a content ranging from 1% to 80% by weight, relative to the total weight of the composition, preferably ranging from 5% to 60% by weight, and preferably ranging from 10% to 50 % in weight.
  • liquid organic compounds or oils which may be present in the liquid organic dispersion medium, there may be mentioned:
  • liquid organic compounds in particular non-silicone or silicone compounds, having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1/2 , preferably less than or equal to 17 (MPa) 1 / 2 ,
  • - dp characterizes the DEBYE interaction forces between permanent dipoles
  • - d H characterizes the specific interaction forces (such as hydrogen bonds, acid / base, donor / acceptor, etc.).
  • liquid fatty substances in particular oils, which can be chosen from natural or synthetic, carbon, hydrocarbon, fluorinated, silicone oils, optionally branched, alone or as a mixture.
  • oils formed by esters of fatty acids and of polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or d 'long chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R 'represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular adipate of diisopropyl.
  • esters of fatty acids and of polyols in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or d 'long chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents the residue of a higher fatty acid containing from 7
  • Mention may also be made of linear, branched and / or cyclic alkanes which may be volatile and in particular paraffin oils, of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones.
  • silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups, and silicone oils volatile, especially cyclical.
  • silicone oils optionally branched, volatile and / or non-volatile.
  • volatile oil an oil capable of evaporating from the skin or the lips in less than an hour, having in particular a vapor pressure, at ambient temperature and atmospheric pressure ranging from 10 ⁇ 3 to 300 mm of Hg ( 0.13 Pa to 40,000 Pa)
  • volatile silicone oil which can be used in the invention, mention may be made of linear or cyclic silicones having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, in particular, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane and decamethyltetrasil can be mentioned.
  • non-volatile silicone oil there may be mentioned non-volatile polydialkylsiloxanes, such as non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, polymethylphenylsiloxanes; polysiloxanes modified with fatty acids (especially C8-C2 ⁇ ) > fatty alcohols (especially Cg-C2 ⁇ ) ° u polyoxyalkylenes
  • PDMS non-volatile polydimethylsiloxanes
  • phenylated silicones such as phen
  • polysiloxanes (in particular polyoxyethylene and / or polyoxypropylene); amino polysiloxanes; polysiloxanes containing hydroxyl groups; fluorinated polysiloxanes comprising a fluorinated group during or at the end of the silicone chain having from 1 to 12 carbon atoms of which all or part of the hydrogen are substituted by fluorine atoms; and their mixtures.
  • liquid monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 is meant aliphatic fatty liquid monoalcohols having from 6 to 30 carbon atoms, the hydrocarbon chain not comprising no substitution group.
  • monoalcohols according to the invention there may be mentioned oleic alcohol, decanol, octyldodecanol and linoleic alcohol.
  • the liquid fatty phase can be a non-silicone liquid fatty phase.
  • non-silicone liquid fatty phase means a fatty phase comprising one or more liquid organic compounds or non-silicone oils, such as those mentioned above, said non-silicone compounds being present mainly in the liquid fatty phase, it that is to say at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or even from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
  • the non-silicone-based liquid organic compounds can in particular be chosen from:
  • non-silicone-based liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2 ,
  • Said non-silicone-based liquid fatty phase may therefore optionally comprise liquid organic compounds or silicone oils, such as those mentioned above, which may be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40 % by weight, or even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
  • the non-silicone liquid fatty phase does not contain liquid organic compounds or silicone oils.
  • the macromoners present in the grafted polymer are advantageously carbon macromonomers as described below.
  • the liquid fatty phase can be a silicone liquid fatty phase.
  • silicone liquid fatty phase means a fatty phase comprising one or more silicone liquid organic compounds or silicone oils such as those described above, said silicone compounds being present mainly in the liquid fatty phase, that is to say at least at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or also from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
  • the liquid organic silicone compounds can be chosen in particular from: - liquid organic compounds, in particular non-silicone or silicone, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2 .
  • Said liquid silicone fatty phase can therefore optionally comprise liquid organic compounds or non-silicone oils, as described above, which can be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40% by weight, even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
  • the liquid silicone fatty phase does not contain non-silicone liquid organic compounds.
  • the choice of monomers constituting the backbone of the polymer, of the macromonomers, the molecular weight of the polymer, the proportion of the monomers and of the macromonomers can be made as a function of the liquid organic dispersion medium so as to advantageously obtain a dispersion of polymer particles grafted in particularly a stable dispersion, this choice can be made by a person skilled in the art.
  • stable dispersion is meant a dispersion which is not liable to form a solid deposit or a liquid / solid phase shift, in particular after centrifugation, for example, at 4000 rpm for 15 minutes.
  • the non-silicone grafted ethylenic polymer forming the particles in dispersion therefore comprises a skeleton insoluble in said dispersion medium and a part soluble in said dispersion medium.
  • the grafted ethylenic polymer can be a random polymer.
  • grafted ethylenic polymer means a polymer capable of being obtained by radical polymerization:
  • grafted acrylic polymer means a polymer capable of being obtained by radical polymerization: - one or more acrylic monomer (s), and optionally one or more additional non-acrylic vinyl monomer (s),
  • the acrylic monomers represent from 50 to 100% by weight, preferably from 55 to 100% by weight (especially from 55 to 95% by weight), preferably from 60 to 100% by weight (especially from 60 to 90% by weight). weight) of the mixture of acrylic monomers + optional non-acrylic vinyl monomers.
  • the acrylic monomers are chosen from monomers whose homopolymer is insoluble in the dispersion medium under consideration, that is to say that the homopolymer is in solid form (or not dissolved) at a greater or equal concentration. at 5% by weight at room temperature (20 ° C) in said dispersion medium.
  • the term "macromonomer having a polymerizable end group” means any polymer comprising on only one of its ends a polymerizable end group capable of reacting during the polymerization reaction with acrylic monomers and optionally additional non-acrylic vinyl monomers constituting the skeleton.
  • the macromonomer makes it possible to form the side chains of the grafted acrylic polymer.
  • the polymerizable group of the macromonomer can advantageously be an ethylenically unsaturated group capable of polymerizing by the radical route with the monomers constituting the skeleton.
  • the macromer is a carbon macromer.
  • carbon macromonomer is meant a non-silicone macromonomer, and in particular an oligomeric macromonomer obtained by polymerization of non-silicone monomer (s) with ethylenic unsaturation, and mainly by polymerization of acrylic and / or non-acrylic vinyl monomers.
  • silicone macromonomer is meant an organopolysiloxane macromonomer, and in particular a polydimethylsiloxane macromonomer.
  • the macromonomer is chosen from macromonomers whose homopolymer is soluble in the dispersion medium under consideration, that is to say completely dissolved at a concentration greater than or equal to 5% by weight and at room temperature in said medium of dispersion.
  • the grafted acrylic polymer comprises a skeleton (or main chain) consisting of a chain of acrylic units resulting from the polymerization in particular of one or more acrylic monomers and side chains (or grafts) resulting from the reaction of the macromonomers, said chains side being covalently linked to said main chain.
  • the skeleton (or main chain) is insoluble in the dispersion medium considered while the side chains (or grafts) are soluble in said dispersion medium.
  • acrylic monomer is meant in the present application monomers chosen from (meth) acrylic acid, esters of (meth) acrylic acid (also called (meth) acrylates), acid amides (methacrylic) (also called (meth) acrylamides).
  • acrylic monomer capable of being used to form the insoluble backbone of the polymer mention may be made, alone or as a mixture, of the following monomers, as well as their salts:
  • Ri in which: - R 1 denotes a hydrogen atom or a methyl group; - R 2 represents a group chosen from:
  • - a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in C1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular with C2-C4 alkylene, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units; a cyclic alkyl group comprising from 3 to 6 carbon atoms, the said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and or possibly comprising one or more substituents chosen from OH and the halogen atoms (F,
  • R 2 mention may be made of the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene 350 EO, trifluoroethyl, group. 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
  • R 3 denotes a hydrogen atom or a methyl group
  • - R and R 5 identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in
  • R 4 represents a hydrogen atom and R 5 represents a 1,1-dimethyl-3-oxobutyl group.
  • alkyl groups which may constitute R and R 5 , there may be mentioned n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
  • acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid.
  • acrylic monomers mention may very particularly be made of methyl, ethyl, propyl, butyl and isobutyl (meth) acrylates; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2- methacrylate hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide; and their salts; and their mixtures.
  • the acrylic monomers are chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, (meth) acrylic acid, dimethylaminoethyl methacrylate, and their mixtures.
  • - vinyl esters of formula: R 6 -COO-CH CH 2 in which R 6 represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or a group cyclic alkyl comprising from 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene and naphthalene type;
  • non-acrylic vinyl monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, and their salts;
  • non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine; - and their mixtures.
  • the acrylic monomers present in the grafted polymer are present in the grafted polymer
  • the acrylic monomers comprise at least
  • the (meth) acrylic acid may be present in a content of at least at least 5% by weight, relative to the total weight of the polymer, in particular ranging from
  • salts there may be mentioned those obtained by neutralization of the acid groups using inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or organic bases of amino alkanol type such as monoethanolamine, diethanolamine, triethanolamine, 2-methyl-2-amino-1-propanol.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or organic bases of amino alkanol type such as monoethanolamine, diethanolamine, triethanolamine, 2-methyl-2-amino-1-propanol.
  • mineral acids there may be mentioned sulfuric acid or hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid.
  • organic acids mention may be made of acids comprising one or more carboxylic, sulphonic or phosphonic groups. They can be linear, branched or cyclic aliphatic acids or even aromatic acids. These acids may also contain one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. Mention may in particular be made of acetic acid or propionic acid, terephthalic acid, as well as citric acid and tartaric acid.
  • the grafted ethylenic polymer does not contain additional non-acrylic vinyl monomers as described above.
  • the insoluble skeleton of the grafted ethylenic polymer is formed only from acrylic monomers as described above. It is understood that these non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with these monomers is insoluble in the dispersion medium.
  • methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, acrylate can be used. isopropyl and isopropyl methacrylate, and mixtures thereof.
  • the additional acrylic monomers can be chosen from:
  • a linear or branched alkyl group comprising from 1 to 6 carbon atoms, said group comprising in its chain one or more oxygen atoms and / or comprising one or more substituents chosen from
  • cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more oxygen atoms and / or possibly comprising one or more substituents chosen from OH and the halogen atoms (F, Cl, Br, I);
  • R ′ 2 mention may be made of the methoxyethyl, ethoxyethyl, trifluoroethyl group; 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
  • acrylic acid methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, their salts, and mixtures thereof.
  • acrylic acid methylacrylic acid.
  • the macromonomers comprise at one end of the chain a polymerizable end group capable of reacting during the polymerization with the acrylic monomers and optionally the additional vinyl monomers, to form the side chains of the grafted ethylenic polymer.
  • Said polymerizable end group may in particular be a vinyl or (meth) acrylate (or (meth) acryloxy) group, and preferably a (meth) acrylate group.
  • the macromonomers are preferably chosen from macromonomers whose homopolymer has a glass transition temperature (Tg) less than or equal to 25 ° C, in particular ranging from - 100 ° C to 25 ° C, preferably ranging from - 80 ° C to 0 ° C.
  • the macromonomers have a weight average molecular mass greater than or equal to 200, preferably greater than or equal to 300, preferably greater than or equal to 500, and more preferably greater than 600.
  • the macromonomers have a weight average molecular weight (Mw) ranging from 200 to 100,000, preferably ranging from 500 to 50,000, preferably ranging from 800 to 20,000, more preferably ranging from 800 to 10,000, and even more preferably ranging from 800 to 6000.
  • Mw weight average molecular weight
  • the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
  • carbon macromonomers mention may in particular be made of:
  • polyolefins having a terminal group containing ethylenic unsaturation in particular having a terminal group (meth) acrylate.
  • macromonomers As an example of such polyolefins, mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: macromonomers of polyethylene, macromonomers of polypropylene, macromonomers of polyethylene / polypropylene copolymer, macromonomers of polyethylene / polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers;
  • Such macromonomers are in particular described in US5625005 which mentions ethylene / butylene and ethylene / propylene macromonomers with reactive (meth) acrylate end group.
  • the polymerized macromonomer (constituting the side chains of the grafted polymer) represents from 0.1 to 15% by weight of the total weight of the polymer, preferably from 0.2 to 10% by weight, and more preferably from 0.3 to 8% by weight.
  • grafted ethylenic polymer dispersed in a non-silicone liquid fatty phase those obtained by polymerization can be used: - methyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in a solvent chosen from isododecane, isononyl isononanoate, octyldodecanol, diisostearyl, a C 12 -C 15 alkyl benzoate (such as Finsolv TN);
  • the grafted polymer has a weight-average molecular mass (Mw) of between 10,000 and 300,000, especially between 20,000 and 200,000, better still between 25,000 and 150,000.
  • Mw weight-average molecular mass
  • the polymers in a given organic dispersion medium, have the capacity to fold in on themselves, thus forming particles of substantially spherical shape, with around the periphery of these particles the deployed side chains, which ensure the stability of these particles.
  • Such particles resulting from the characteristics of the grafted polymer have the particularity of not agglomerating in said medium and therefore of self-stabilizing and of forming a dispersion of particularly stable polymer particles.
  • the grafted ethylenic polymers of the dispersion can form nanometric particles, of average size ranging from 10 to 400 nm, preferably from 20 to 200 nm.
  • the particles of polymer grafted in dispersion are particularly stable and therefore unlikely to form agglomerates.
  • the dispersion of grafted polymer can therefore be a stable dispersion and does not form sediments, when it is placed for a prolonged period (for example 24 hours) at room temperature (25 ° C).
  • the dispersion of particles of grafted polymer has a content of dry matter (or dry extract) in polymer which can range from 40% to 70% by weight of dry matter, in particular ranging from 45% to 65% by weight.
  • the dispersion of grafted polymer particles can be prepared by a process comprising a step of radical copolymerization, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.
  • the liquid organic dispersion medium can be identical to or different from the polymerization medium.
  • the copolymerization can be carried out in the presence of a polymerization initiator.
  • the polymerization initiators can be radical initiators.
  • such a polymerization initiator can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate; diazotized compounds such as azobisisobutyronitrile, azobisdimethylvalero-nitrile.
  • the reaction can also be initiated using photoinitiators or by radiation such as UV, neutrons or plasma.
  • the organic polymerization medium is introduced into a reactor of a size appropriate to the quantity of polymer that is to be produced, and / or additional vinyls, which will constitute, after polymerization, the insoluble skeleton, all of the macromonomer (which will constitute the side chains of the polymer) and part of the polymerization initiator.
  • the reaction medium forms a relatively homogeneous medium.
  • the reaction medium is then stirred and heated to a temperature to obtain a polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion with a milky appearance.
  • a mixture consisting of the remaining part of the monomers and of the polymerization initiator is then added.
  • the medium stabilizes in the form of a milky dispersion, the dispersion comprising particles of polymers stabilized in the medium in which they were created, said stabilization being due to the presence , in the polymer, of side chains soluble in said dispersion medium.
  • the grafted polymer may be present in the composition according to the invention in a dry matter (or active material) content ranging from 1 to 70% by weight relative to the total weight of the composition, better still from 5 to 60% by weight, preferably ranging from 6 to 45% and better still ranging from 8 to 40% by weight.
  • composition according to the invention may also comprise at least fatty substances which are solid at room temperature, in particular chosen from waxes, pasty fatty substances, gums and their mixtures. These fatty substances can be of animal, vegetable, mineral or synthetic origin.
  • composition according to the invention may comprise a wax or a mixture of waxes.
  • the wax considered in the context of the present invention is generally a lipophilic compound, solid at room temperature (25 ° C), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C up to 120 ° C.
  • the waxes suitable for the invention can have a melting point greater than approximately 45 °, and in particular greater than 55 ° C.
  • the melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METLER.
  • DSC. differential scanning calorimeter
  • a 15 mg sample of product placed in a crucible is subjected to a first temperature rise ranging from 0 ° C to 120 ° C, at the heating rate of 10 ° C / minute, then is cooled from 120 ° C to 0 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise ranging from 0 ° C to 120 ° C at a heating rate of 5 ° C / minute.
  • the variation in the difference in power absorbed by the empty crucible and by the crucible containing the product sample is measured as a function of the temperature.
  • Point of melting of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of the temperature.
  • the waxes capable of being used in the compositions according to the invention are chosen from waxes, solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin and their mixtures.
  • the wax can also have a hardness ranging from 0.05 MPa to 30 MPa, and preferably ranging from 6 MPa to 15 MPa.
  • the hardness is determined by measuring the compressive force measured at 20 ° C using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm. moving at the measuring speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm.
  • the measurement protocol is as follows:
  • the wax is melted at a temperature equal to the melting point of the wax + 20 ° C.
  • the melted wax is poured into a container 30 mm in diameter and 20 mm deep.
  • the wax is recrystallized at room temperature (25 ° C) for 24 hours, then the wax is stored for at least 1 hour at 20 ° C before carrying out the hardness measurement.
  • the hardness value is the maximum compression force measured divided by the surface area of the texturometer cylinder in contact with the wax.
  • hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes
  • rice wax Carnauba wax, Candellila wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax
  • montan wax microcrystalline waxes, paraffins and ozokerite
  • polyethylene waxes waxes obtained by the Fisher-Tropsch synthesis and waxy copolymers and their esters. Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, of C8-C32.
  • JOJOBA-50 ® hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di- (trimethylol-) tetrastearate
  • HEST 2T-4S di- (trimethylol-1, 1, 1 propane) tetrabehenate sold under the name HEST 2T- 4B by the company HETERENE.
  • silicone waxes such as alkyl or alkoxy-dimethicone having
  • the compositions according to the invention can comprise at least one so-called sticky wax, that is to say having a stickiness greater than or equal to 0.7 Ns and a hardness less than or equal to 3.5 MPa.
  • sticky wax can in particular make it possible to obtain a cosmetic composition which is easily applied to keratin fibers, having good adhesion to keratin fibers and which leads to the formation of a smooth, homogeneous makeup. and thickener.
  • the sticky wax used may in particular have a tack ranging from 0.7 Ns to 30 Ns, in particular greater than or equal to 1 Ns, in particular ranging from 1 Ns to 20 Ns, in particular greater than or equal to 2 Ns, in particular ranging from 2 Ns to 10 Ns, and in particular ranging from 2
  • the stickiness of the wax is determined by measuring the evolution of the force (compression force or stretching force) as a function of time, at 20 ° C. using the texturometer sold under the name "TA-TX2i ® ”by the company RHEO, equipped with a mobile in acrylic polymer in the shape of a cone forming an angle of 45 °.
  • the measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 10 ° C. The melted wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C) for 24 hours so that the surface of the wax is flat and smooth, then the wax is stored for at least 1 hour at 20 ° C before measuring the tights.
  • the mobile of the texturometer is moved at the speed of 0.5 mm / s, then enters the wax to a penetration depth of 2 mm. When the mobile has penetrated into the wax to the depth of 2 mm, the mobile is held fixed for 1 second (corresponding to the relaxation time) then is removed at the speed of 0.5 mm / s.
  • the force decreases sharply until it becomes zero, then, when the mobile is removed, the force (stretching force) becomes negative and then increases again towards the value 0.
  • the tights corresponds to the integral of the force curve as a function of time for the part of the curve corresponding to the negative values of the force (stretching force). The value of the tights is expressed in N.s.
  • the sticky wax that can be used generally has a hardness less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, in particular ranging from 0.05 MPa to 3 MPa, or even ranging from 0, 1 MPa to 2.5 MPa.
  • the hardness is measured according to the protocol described above.
  • n is an integer ranging from 18 to 38, or a mixture of compounds of formula (II).
  • Such a wax is sold in particular under the names “Kester Wax K 82 P ® " and “Kester Wax K 80 P ®” by the company KOSTER KEUNEN.
  • the waxes mentioned above generally have a starting melting point below 45 ° C.
  • the wax (es) can be present in the form of an aqueous microdispersion of wax.
  • aqueous wax microdispersion is understood to mean an aqueous dispersion of wax particles, in which the size of said wax particles is less than or equal to approximately 1 ⁇ m.
  • Wax microdispersions are stable dispersions of colloidal wax particles, and are described in particular in "Microemulsions Theory and Practice", L.M. Prince Ed., Académie Press (1977) pages 21-32.
  • these wax microdispersions can be obtained by melting the wax in the presence of a surfactant, and optionally part of the water, then progressive addition of hot water with stirring. The intermediate formation of a water-in-oil type emulsion is observed, followed by a phase inversion with final production. of an oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal wax particles is obtained.
  • the wax microdispersion can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high pressure homogenizer, turbines.
  • the particles of the wax microdispersion preferably have mean dimensions of less than 1 ⁇ m (in particular ranging from 0.02 ⁇ m to 0.99 ⁇ m), preferably less than 0.5 ⁇ m (in particular ranging from 0.06 ⁇ m to 0 , 5 ⁇ m).
  • These particles consist essentially of a wax or a mixture of waxes. They may, however, in a minor proportion comprise oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active.
  • pasty fatty substance means a lipophilic fatty compound comprising at the temperature of 23 ° C. a liquid fraction and a solid fraction.
  • Said pasty compound preferably has a hardness at 20 ° C ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.
  • the hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyzer (for example TA-XT2i from Rhéo) equipped with a stainless steel cylinder of 2 mm in diameter.
  • the hardness measurement is carried out at 20 ° C in the center of 5 samples.
  • the cylinder is introduced into each sample at a pre-speed of 1 mm / s and then at a measurement speed of 0.1 mm / s, the penetration depth being 0.3 mm.
  • the value recorded for the hardness is that of the maximum peak.
  • the liquid fraction of the pasty compound. Measured at 23 ° C. preferably represents 9 to 97% by weight of the compound. This liquid fraction at 23 ° C preferably represents between 15 and 85%, more preferably between 40 and 85% by weight.
  • the liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed to
  • the enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state.
  • the pasty compound is said to be in the solid state when all of its mass is in crystalline solid form.
  • the pasty compound is said to be in the liquid state when all of its mass is in liquid form.
  • the enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10 ° C per minute, according to ISO 11357-3: 1999.
  • the enthalpy of fusion of the pasty compound is the amount of energy required to bring the compound from the solid state to the liquid state. It is expressed in J / g.
  • the enthalpy of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to go from the solid state to the state it presents at 23 ° C consisting of a liquid fraction and a solid fraction.
  • the liquid fraction of the pasty compound measured at 32 ° C. preferably represents from 30 to 100% by weight of the compound, preferably from 80 to 100%, more preferably from 90 to 100% by weight of the compound.
  • the temperature at the end of the melting range of the pasty compound is less than or equal to 32 ° C.
  • the liquid fraction of the pasty compound measured at 32 ° C is equal to the ratio of the enthalpy of fusion consumed at 32 ° C to the enthalpy of fusion of the pasty compound.
  • the enthalpy of fusion consumed at 32 ° C is calculated in the same way as the enthalpy of fusion consumed at 23 ° C.
  • the gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and pasty bodies are generally hydrocarbon compounds such as lanolines and their derivatives or even PDMSs.
  • PDMS polydimethylsiloxanes
  • the nature and quantity of the solid bodies are a function of the mechanical properties and of the desired textures.
  • the composition may contain from 0.1 to 50% by weight of waxes, relative to the total weight of the composition, better from 1 to 40% and even better still from 5 to 30% by weight.
  • the composition may comprise, in addition to the polymer dispersed in the liquid fatty phase described above according to the invention, an additional polymer such as a film-forming polymer.
  • a film-forming polymer means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
  • film-forming polymers which can be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures.
  • film-forming polymer mention may in particular be made of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.
  • the composition according to the invention may also comprise one or more coloring materials chosen from water-soluble dyes, and pulverulent coloring materials such as pigments, nacres and flakes well known to those skilled in the art.
  • the coloring matters can be present, in the composition, in a content ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
  • the term “pigments” should be understood to mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.
  • the pigments can be white or colored, mineral and / or organic.
  • mineral pigments mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder.
  • organic pigments mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
  • effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being whether or not covered with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metallic oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures.
  • the pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, mica titanium coated with in particular blue ferric or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on oxychloride bismuth. .
  • Interferential pigments can also be used, in particular with liquid crystals or multilayers.
  • an object of the present invention is a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase and a pulverulent coloring matter, in particular in the form of pigments. .
  • the liposoluble dyes are for example Sudan red, D&C Red 17, D&C Green 6, ⁇ -carotene, soybean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C orange 5, quinoleine yellow, annatto.
  • the water-soluble dyes are, for example, beet juice, methylene blue, disodium salt of culvert, disodium salt of alizarin green, quinole yellow, trisodium salt of amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, disodium salt of fuchsin, xanthophyll.
  • the composition according to the invention may comprise at least one filler, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. weight.
  • fillers it is necessary to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the middle of the composition regardless of the temperature at which the composition is produced. These charges are used in particular to modify the rheology or the texture of the composition.
  • the fillers can be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) (Orgasol® from Atochem), poly- ⁇ -alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon®) ), lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), of acrylic acid copolymers (Polytrap® of the society
  • silicone resin microbeads Dow Corning and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro carbonate, hydroxyapatite, microspheres hollow silica (Silica Beads® by Maprecos), glass or ceramic microcapsules, metallic soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example stearate zinc, magnesium or lithium, zinc laurate, magnesium myristate.
  • composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, filters sunscreen, surfactants, antioxidants, fibers, anti-hair loss agents, eyelash care agents, dandruff agents, propellants, or mixtures thereof.
  • fiber is meant an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed.
  • the L / D ratio is chosen from the range going from 3.5 to
  • 2500 preferably from 5 to 500, and better still from 5 to 150.
  • the fibers have a length ranging from 1 ⁇ m to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm.
  • the fibers which can be used in the composition of the invention can be chosen from rigid or non-rigid fibers, they can be of synthetic or natural, mineral or organic origin.
  • a usable fibers in the composition according to the invention mention may be made of non-rigid fibers such as polyamide fibers (Nylon ®) or rigid fibers such as polyimide-amide fibers such as those sold under the trademark "KERMEL ",”
  • Kevlar TECH by the company RHODIA or poly- (p-phenylene-terephthalamide) (or aramid) especially sold under the name Kevlar ® by the company DUPONT
  • the fibers may be present in the composition according to the invention in a content ranging from 0.1 to 10% by weight, better still from 0.5 to 5% by weight relative to the total weight of the composition.
  • the gelling agents which can be used in the compositions according to the invention can be hydrophilic, lipophilic, organic or inorganic, polymeric or molecular gelling agents.
  • clays optionally modified such as hectorites modified with ammonium chloride of C 10 to C 22 fatty acid, such as hectorite modified with di-stearyl di-methyl ammonium chloride.
  • hectorites modified with ammonium chloride of C 10 to C 22 fatty acid such as hectorite modified with di-stearyl di-methyl ammonium chloride.
  • di-stearyl di-methyl ammonium chloride such as, for example, that marketed under the name of "Bentone 38V ® " by the company ELEMENTIS.
  • pyrogenic silica optionally treated hydrophobically at the surface, the particle size of which is less than 1 ⁇ m. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.
  • the hydrophobic groups can be:
  • Silicas thus treated are named “Silica Silylate” according to the CTFA (6 th edition, 1995). They are for example marketed under the references “Aerosil R812 ®” by the company DEGUSSA, "CAB-O-SIL TS-530 ® " by the company CABOT,
  • Silicas thus treated are called “Silica dimethyl silylate” according to the CTFA (6 th edition, 1995). They are for example marketed under the references “Aerosil R972 ® “, and “Aerosil R974 ® “ by the company DEGUSSA, "CAB-O-SIL TS-610 ® “ and “CAB-O-SIL TS-720 ® " by the CABOT company.
  • the hydrophobic pyrogenic silica has in particular a particle size which can be nanometric to micrometric, for example ranging from approximately 5 to 200 nm.
  • the polymeric organic lipophilic gelling agents are, for example, elastomeric polyorganosiloxanes partially or totally crosslinked, three-dimensional structure, such as those sold under the names "KSG6 ®", “KSG16 ®” and “KSG18 ®” by the company Shin-Etsu, for “Trefil E-505C ® “ and “Trefil E-506C ®” by the company DOW-CORNING, from “Gransil SR-CYC ® ", "SR
  • the block copolymers of "diblock” or “triblock” of the polystyrene / polyisoprene or polystyrene / polybutadiene type such as those marketed under the name “Luvitol HSB ®” by the company BASF, of the polystyrene / copoly (ethylene-propylene) type such as those sold under the name “Kraton ®” by Shell Chemical Co., or the polystyrene / copoly (ethylene-butylene).
  • lipophilic gelling agents which can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those marketed under the names of "Rheopearl TL ® " or “Rheopearl KL ®” by the company CHIBA FLOUR.
  • the lipophilic gelling agents can be present in the composition according to the invention in a content ranging from 0.05 to 40% by weight relative to the total weight of the composition, preferably from 0.5 to 20% and better still from 1 to 15 % in weight.
  • hydrophilic or water-soluble gelling agents mention may be made of: homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the names "VERSICOL F” or "VERSICOL K” by the company ALLIED COLLOID,
  • SYNTHALEN K the copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names "RETEN” by the company HERCULES, the sodium polymethacrylate sold under the name “DARVAN N ° 7" by the company VANDERBILT, the sodium salts of polyhydroxycarboxylic acids sold under the name "HYDAGEN F” by the company HENKEL, the polyacrylic acid / alkyl acrylate copolymers of the PEMULEN type, AMPS (Polyacrylamidomethyl propane sulfonic acid partially neutralized with ammonia and highly crosslinked) sold by the company CLARIANT,
  • the AMPS / acrylamide copolymers of the SEPIGEL or SIMULGEL type sold by the company SEPPIC and the AMPS / methacrylate copolymers of polyoxyethylenated alkyl (crosslinked or not) and their mixtures.
  • water-soluble gelling polymers examples include: - proteins such as proteins of plant origin such as wheat, soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as quaternized derivatives of cellulose; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; vinylpyrrolidone and caprolactam copolymers; polyvinyl alcohol; associative polyurethanes such as the polymer
  • Rheolate 244 sold by the company RHEOX can also use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from the company RHOM & HAAS, or even Borchigel LW 44 from the company BORCHERS, polymers of natural origin , possibly modified, such as: - gum arabic, guar gum, xanthan derivatives, karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; shellac resin, sandara gum, dammars, elemis, copals; deoxyribonucleic acid; muccopolysaccharides such as hyaluronic acid, chondroitins sulfate, and mixtures thereof.
  • polymers of natural origin possibly modified, such as: - gum arabic, guar gum, xanthan derivatives, karaya gum; alginates and carrageenans;
  • the hydrophilic gelling agents can be present in the composition according to the invention in a content ranging from 0.05 to 20% by weight relative to the total weight of the composition, preferably from 0.5 to 10% and better still from 0.8 at 5% by weight.
  • composition according to the invention may contain emulsifying surfactants present in particular in a proportion ranging from 0.5 to 30% by weight relative to the total weight of the composition, better from 2 to 15% and better still from 3 to 10%.
  • surfactants can be chosen from anionic, cationic or nonionic surfactants.
  • the surfactants preferably used in the composition according to the invention are chosen from: a) nonionic surfactants with an HLB greater than or equal to 8 at 25 ° C., used alone or as a mixture; mention may in particular be made of: oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of glycerol; oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular C8-C24, and preferably C12-C18 alcohol) such as oxyethylenated ether cetearyl alcohol with 30 oxyethylenated groups (CTFA name "Ceteareth-30”) and the oxyethylenated ether of the mixture of C12-C
  • PE / F127 "by the company ICI, and their mixtures. And their mixtures, b) nonionic surfactants with an HLB of less than 8 at 25 ° C., optionally combined with one or more nonionic surfactants with an HLB of more than 8 to 25 ° C.
  • esters and ethers of dares such as sucrose stearate, sucrose cocoate, sorbitan stearate and their mixtures such as Ariatone 2121 sold by the company ICI; esters fatty acids (in particular C8-C24, and preferably C16-C22) and polyol, in particular glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name TEGIN M by the company GOLDSCHMIDT, glyceryl laurate such as the product sold under the name IMWITOR 312 by the company HULS, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate; the mixture of cyclomethicone / dimethicone copolyol v coated under the name "Q2-3225C" by the company DOW CORNING.
  • esters and ethers of dares such as sucrose
  • Anionic surfactants such as: the salts of C 16 -C 30 fatty acids, in particular those derived from amines, such as triethanolamine stearate; the salts of polyoxyethylenated fatty acids, in particular those derived from amines or the alkaline salts, and their mixtures; phosphoric esters and their salts such as "DEA oleth-10 phosphate” (Crodafos N 10N from the company CRODA); sulfosuccinates such as “Disodium PEG-5 citrate lauryl sulfosuccinate” and “Disodium ricinoleamido MEA sulfosuccinate” alkyl ether sulfates, such as sodium lauryl ether sulfate; isethionates; acylglutamates such as "Disodium hydrogenated tallow glutamate"
  • triethanolamine stearate is particularly suitable for the invention.
  • the latter is generally obtained by simple mixing of stearic acid and triethanolamine.
  • Surfactants are preferably used which make it possible to obtain an oil-in-water or wax-in-water emulsion.
  • composition according to the invention can comprise an aqueous medium, constituting an aqueous phase, which can form the continuous phase of the composition.
  • the aqueous phase can consist essentially of water; it can also comprise a mixture of water and water-miscible solvent (miscibility in water greater than 50% by weight at 25 ° C) such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol, Pisopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes e f
  • the aqueous phase water and optionally the water-miscible solvent
  • the composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of two-phase lotion or multiphase, spray, powder, paste, in particular flexible paste (in particular paste having a dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s under a shear speed of 200 s "1 , after 10 minutes of measurement in cone / plane geometry).
  • the composition can be anhydrous, for example it can be an anhydrous paste or stick.
  • the composition can be a leave-in composition.
  • the invention also relates to a cosmetic assembly comprising: i) a container delimiting at least one compartment, said container being closed by a closing element; and ii) a composition disposed inside said compartment, the composition being according to any one of the preceding claims.
  • the container can be in any suitable form. It can in particular be in the form of a bottle, a tube, a pot, a case, a box, a sachet or a case.
  • the closure element may be in the form of a removable stopper, a cover, a cover, a tearable strip, or a capsule, in particular of the type comprising a body fixed to the container and an articulated cap. on the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.
  • the container can be associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire.
  • a twisted brush is described in particular in US Pat. No. 4,887,622.
  • It can also be in the form of a comb comprising a plurality of application elements, obtained in particular by molding. Such combs are described for example in patent FR 2 796 529.
  • the applicator can be in the form of a brush, as described for example in patent FR 2 722 380.
  • the applicator can be in the form of a block of foam or elastomer, a felt, or a spatula.
  • the applicator can be free (puff or sponge) or integral with a rod carried by the closure element, as described for example in US patent 5,492,426.
  • the applicator can be integral with the container, as described for example the patent FR 2 761 959.
  • the product can be contained directly in the container, or indirectly.
  • the product can be placed on an impregnated support, in particular in the form of a wipe or a tampon, and placed (individually or several) in a box or in a sachet.
  • an impregnated support in particular in the form of a wipe or a tampon
  • Such a support incorporating the product is described for example in application WO 01/03538.
  • the closure element can be coupled to the container by screwing.
  • the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, tightening, welding, bonding, or by magnetic attraction.
  • snap-fastening is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the non-elastically constrained position of said portion after crossing the bead or cord.
  • the container can be at least partly made of thermoplastic material.
  • thermoplastic materials mention may be made of polypropylene or polyethylene.
  • the container is made of non-thermoplastic material, in particular glass or metal (or alloy).
  • the container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.
  • the container may include means for causing or facilitating the distribution of the composition.
  • the container may have deformable walls so as to cause the exit of the composition in response to an overpressure inside the container, which overpressure is caused by elastic (or inelastic) crushing of the walls of the container. .
  • the latter can be driven by a piston mechanism.
  • the container may include a mechanism, in particular rack and pinion, or with a threaded rod, or with a helical ramp, and able to move a stick in the direction of said opening.
  • a mechanism is described for example in patent FR 2 806 273 or in patent FR 2 775 566.
  • Such a mechanism for a liquid product is described in the patent
  • the container may consist of a housing with a bottom delimiting at least one housing containing the composition, and a cover, in particular articulated on the bottom, and capable of covering said bottom at least in part.
  • a cover in particular articulated on the bottom, and capable of covering said bottom at least in part.
  • the container can be equipped with a wringer disposed near the opening of the container.
  • a wringer makes it possible to wipe the applicator and possibly, the rod of which it may be integral.
  • Such a wringer is described for example in patent FR 2 792 618.
  • the composition can be at atmospheric pressure inside the container (at room temperature) or pressurized, in particular by means of a propellant gas (aerosol).
  • a propellant gas as an aerosol
  • the container is fitted with a valve (of the type used for aerosols).
  • Examples 1 and 2 illustrate the preparation of polymers in accordance with the invention, capable of forming a dispersion of particles in an organic medium under consideration.
  • the average molar masses by weight (Mw) and by number (Mn) of the polymer are determined, the glass transition temperature of the polymer, the dry matter (or dry extract) content of the dispersion and size of the polymer particles.
  • the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
  • the measurement of the glass transition temperature (Tg) is carried out according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range between -100 ° C and +150 ° C at a heating rate of 10 ° C / min in 150 ⁇ l aluminum crucibles.
  • the crucibles are prepared as follows: 100 ⁇ l of the dispersion obtained is introduced into an aluminum crucible of 150 ⁇ l and the solvent is allowed to evaporate for 24 hours at room temperature and at 50% relative humidity. The operation is repeated and then the crucible is introduced into the Mettler DSC30 calorimeter.
  • the rate of dry matter (or dry extract), that is to say the content of non-volatile matter, can be measured in different ways: for example, the methods by drying in an oven or the methods by drying by exposure to infrared radiation.
  • the dry matter content of the polymer dispersion obtained is measured by heating the sample by infrared rays from 2 ⁇ m to 3.5 ⁇ m in wavelength.
  • the substances contained in the composition which have a high vapor pressure evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition.
  • the measurement protocol is as follows: approximately 1 g of the dispersion is spread over a metal dish. This, after introduction into the desiccator, is subjected to a temperature set point of 120 ° C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance.
  • the dry matter content is calculated as follows:
  • Dry extract 100 x (dry mass / wet mass).
  • Particle sizes can be measured by different techniques: we can cite in particular light scattering techniques (dynamic and static), Coulter counter methods, measurements by sedimentation speed (related to size via the law of Stokes) and microscopy. These techniques make it possible to measure a particle diameter and for some of them a particle size distribution.
  • the sizes and size distributions of the particles of the compositions according to the invention are measured by static light scattering using a commercial granulometer of the MasterSizer 2000 type from Malvern. The data is processed on the basis of Mie diffusion theory. This theory, exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an "effective" diameter of particles. This theory is notably described in the work of Van de Hulst, H.C., "Light Scattering by Smail Particles," Chapters 9 and 10, Wiley, New York, 1957.
  • composition is characterized by its mean “effective” diameter in volume D [4.3], defined as follows: ⁇ V d,
  • Vj represents the volume of particles of effective diameter dj. This parameter is described in particular in the technical documentation of the granulometer. The measurements are carried out at 25 ° C., on a dispersion of dilute particles, obtained from the composition as follows: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) rest of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant.
  • the "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.42 for particles.
  • This example illustrates the preparation of a dispersion of particles of a polymer in isododecane, said polymer being obtained by polymerization of methyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group (Kraton L-1253 ).
  • the grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
  • This example illustrates the preparation of a polymer forming a dispersion of particles in a carbonaceous solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group ( Kraton L-1253).
  • the grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
  • the characteristics of the polymer and of the particles formed by said polymer are: following:
  • composition was prepared according to the same procedure as that of
  • This composition can be prepared in a standard manner by hot formation of a wax in water emulsion.
  • the fatty phase is heated (phase A) containing the wax and the stearic acid until all the constituents have completely melted. Then, the polymer dispersion of Example 2 and the pigments are incorporated with stirring in the oily phase.
  • the aqueous phase (phase B) containing the neutralizer (Triethanolamine), the gelling polymers are brought to a temperature at least equal to the temperature of the phase fat. The aqueous phase is then added to the oily phase, with vigorous stirring (3000rpm), to form the hot emulsion. Agitation and temperature are maintained for approximately 30 minutes.

Abstract

The invention relates to a cosmetic composition comprising, in a cosmetically-acceptable medium, at least one dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase. The invention can be used in make-up and in the care of keratin materials, such as the skin and lips.

Description

Composition cosmétique non transfert comprenant une dispersion de particules d'un polymère éthylenique greffé non silicone dans une phase grasse liquide Non-transfer cosmetic composition comprising a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase
La présente invention a pour objet une composition cosmétique comprenant une dispersion de particules d'un polymère éthylenique greffé non silicone dans une phase grasse liquide, destinée à être appliquée sur les matières kératiniques d'êtres humains, comme la peau, les lèvres, les ongles, les fibres kératiniques tels que les cils, les sourcils, les cheveux.The subject of the present invention is a cosmetic composition comprising a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase, intended to be applied to keratin materials of human beings, such as the skin, the lips, the nails. , keratin fibers such as eyelashes, eyebrows, hair.
La composition selon l'invention peut être une composition de maquillage ou une composition de soin des matières kératiniques, en particulier de la peau, des lèvres et des fibres kératiniques, notamment des cils, et de préférence une composition de maquillage.The composition according to the invention may be a makeup composition or a care composition for keratin materials, in particular the skin, lips and keratin fibers, in particular eyelashes, and preferably a makeup composition.
La composition de maquillage peut être un produit de maquillage des lèvres (rouge à lèvres), un fond de teint, un fard à paupières, un fard à joue, un produit anticernes, un eye-liner, un produit de maquillage du corps, un mascara, un vernis à ongles, un produit de maquillage des cheveux.The makeup composition can be a lip makeup product (lipstick), a foundation, an eyeshadow, a blush, a concealer product, an eyeliner, a body makeup product, a mascara, nail polish, hair makeup product.
La composition de soin peut être un produit de soin de la peau du corps et du visage, notamment un produit solaire, un produit de coloration de la peau (tel qu'un autobronzant). La composition peut être également un produit capillaire, notamment pour le maintien de la coiffure ou la mise en forme des cheveux ou encore un produit de soin des cils .The care composition may be a care product for the skin of the body and the face, in particular a sun care product, a product for coloring the skin (such as a self-tanner). The composition can also be a hair product, in particular for maintaining the hairstyle or shaping the hair, or even an eyelash care product.
Les compositions de rouge à lèvres et fond de teint sont couramment employées pour apporter une couleur esthétique aux lèvres ou à la peau, notamment au visage. Ces produits de maquillage contiennent généralement des phases grasses telles que des cires et des huiles, des pigments et/ou charges et éventuellement des additifs comme des actifs cosmétiques ou dermatologiques.Lipstick and foundation compositions are commonly used to provide an aesthetic color to the lips or to the skin, in particular to the face. These makeup products generally contain fatty phases such as waxes and oils, pigments and / or fillers and optionally additives such as cosmetic or dermatological active agents.
Ces compositions, lorsqu'elles sont appliquées sur la peau, présentent l'inconvénient de transférer, c'est-à-dire de se déposer au moins en partie, en laissant des traces, sur certains supports avec lesquels elles peuvent être mises en contact et notamment un verre, une tasse, une cigarette, un vêtement ou la peau. Il s'ensuit une persistance médiocre du film appliqué, nécessitant de renouveler régulièrement l'application de la composition de fond de teint ou de rouge à lèvres. Par ailleurs, l'apparition de ces traces inacceptables notamment sur les cols de chemisier peut écarter certaines femmes de l'utilisation de ce type de maquillage.These compositions, when applied to the skin, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact. and in particular a glass, a cup, a cigarette, a garment or the skin. It follows a mediocre persistence of the applied film, requiring to regularly renew the application of the foundation or lipstick composition. Furthermore, the appearance of these unacceptable traces, in particular on shirt collars, may exclude certain women from the use of this type of makeup.
On recherche donc des compositions de maquillage pour les lèvres et la peau dites « sans transfert » qui présentent l'avantage de former un dépôt qui ne se dépose pas, au moins en partie, sur les supports avec lesquels elles sont mises en contact (verre, vêtements, cigarette, tissus).So we look for make-up compositions for the lips and the skin called "without transfer" which have the advantage of forming a deposit which does not settle, at least in part, on the supports with which they are brought into contact (glass , clothes, cigarette, fabrics).
Pour limiter le transfert des compositions cosmétiques, il est connu d'employer des huiles volatiles , notamment à des teneurs supérieures à 40 % en poids. Ces huiles volatiles présentes en grande quantité rendent le produit de maquillage, notamment le rouge à lèvres, inconfortable pour l'utilisatrice : le dépôt de maquillage confère une sensation de dessèchement et de tiraillement.To limit the transfer of cosmetic compositions, it is known to use volatile oils, in particular at contents greater than 40% by weight. These volatile oils present in large quantities make the makeup product, in particular the lipstick, uncomfortable for the user: the deposit of makeup confers a feeling of drying and tightness.
Il est également connu des produits sous forme de deux compositions distinctes à appliquer l'une sur l'autre sur les lèvres pour obtenir un maquillage sans transfert. Par exemple, le produit LIP FINITY de MAX FACTOR est un produit bi-couche dont la composition de base (dite base coat) contient une résine de silicone et des huile volatiles, et la composition de surface (dite top coat) contient un ester de saccharose (comme décrit dans la demande WO 97/17057) pour améliorer le confort du produit de maquillage non transfert. Toutefois, l'application de deux compositions pour se maquiller peut être rédhibitoire pour certaines utilisatrices.Products are also known in the form of two separate compositions to be applied one on the other on the lips to obtain makeup without transfer. For example, LIP FINITY by MAX FACTOR is a two-layer product, the base composition of which (called base coat) contains a silicone resin and volatile oils, and the surface composition (so-called top coat) contains a sucrose ester (as described in application WO 97/17057) to improve the comfort of the non-transfer makeup product. However, the application of two makeup compositions can be prohibitive for some users.
La présente invention a pour but de fournir une nouvelle voie de formulation d'une composition cosmétique, notamment de maquillage, permettant d'obtenir un dépôt ayant de bonnes propriétés de non transfert, notamment sans utiliser un taux important d'huiles volatiles, et ce, sans requérir l'application de deux compositions distinctes pour l'obtention du résultat.The present invention aims to provide a new way of formulating a cosmetic composition, in particular make-up, making it possible to obtain a deposit having good non-transfer properties, in particular without using a high rate of volatile oils, and this , without requiring the application of two separate compositions to obtain the result.
L'invention a également pour but de fournir une composition cosmétique, notamment de maquillage, permettant d'obtenir un dépôt sur la peau, les lèvres ou les fibres kératiniques confortable.The invention also aims to provide a cosmetic composition, in particular make-up, making it possible to obtain a comfortable deposit on the skin, the lips or the keratin fibers.
Les inventeurs ont découvert qu'il est possible d'obtenir une telle composition en utilisant une dispersion de particules d'un polymère éthylenique greffé non silicone dans une phase grasse liquide telle que décrite ci-après. La composition permet d'obtenir un dépôt, notamment un maquillage des matières kératiniques, en particulier de la peau, des lèvres ou des fibres kératiniques, présentant de bonnes propriétés de non transfert. De plus, le dépôt obtenu sur la peau ou les lèvres ne provoque pas de sensation de dessèchement ou de tiraillement pour l'utilisatrice : le dépôt est donc confortable.The inventors have discovered that it is possible to obtain such a composition by using a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase as described below. The composition makes it possible to obtain a deposit, in particular a make-up of keratin materials, in particular of the skin, the lips or keratin fibers, having good non-transfer properties. In addition, the deposit obtained on the skin or the lips does not cause a feeling of dryness or tightness for the user: the deposit is therefore comfortable.
De façon plus précise, la présente invention a donc pour objet une composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, au moins une dispersion de particules, de préférence solides, d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide telle que décrite ci après, la composition étant notamment telle que définie ci-après.More specifically, the present invention therefore relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one dispersion of particles, preferably solid, of a non-grafted ethylenic polymer. silicone in a liquid fatty phase as described below, the composition being in particular as defined below.
Avantageusement, selon un premier mode de réalisation de la composition selon l'invention, le polymère est tel que lorsqu'il est dispersé en quantité suffisante dans la composition, cette dernière est apte à former un dépôt ayant un transfert inférieur ou égal à 35 %.Advantageously, according to a first embodiment of the composition according to the invention, the polymer is such that when it is dispersed in sufficient quantity in the composition, the latter is capable of forming a deposit having a transfer less than or equal to 35% .
Avantageusement, la composition selon l'invention est apte à former un dépôt ayant un transfert inférieur ou égal à 30 %, de préférence inférieur ou égal à 25 %, de préférence inférieur ou égal à 20 %, de préférence inférieur ou égal à 15 %, de préférence inférieur ou égal à 10 %, de préférence inférieur ou égal à 5 %.Advantageously, the composition according to the invention is capable of forming a deposit having a transfer less than or equal to 30%, preferably less than or equal to 25%, preferably less than or equal to 20%, preferably less than or equal to 15% , preferably less than or equal to 10%, preferably less than or equal to 5%.
L'invention a également pour objet un procédé cosmétique de maquillage ou de soin non thérapeutique des matières kératiniques, en particulier de la peau, des lèvres ou des fibres kératiniques, comprenant l'application sur les matières kératiniques, en particulier sur la peau ou les lèvres, d'une composition telle que définie précédemment.The subject of the invention is also a cosmetic process for making up or for non-therapeutic care of keratin materials, in particular of the skin, lips or keratin fibers, comprising the application to keratin materials, in particular on the skin or lips, of a composition as defined above.
L'invention a également pour objet l'utilisation d'une composition telle que définie précédemment pour obtenir un dépôt non transfert, notamment un maquillage, sur les matières kératiniques, en particulier sur la peau, les lèvres ou les fibres kératiniques.The subject of the invention is also the use of a composition as defined above to obtain a non-transfer deposit, in particular make-up, on keratin materials, in particular on the skin, lips or keratin fibers.
L'invention a également pour objet l'utilisation d'une dispersion de particules d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide telle que défini précédemment, dans une composition cosmétique comprenant un milieu liquide organique cosmétiquement acceptable, pour obtenir un dépôt, notamment un maquillage, non transfert sur les matières kératiniques, en particulier sur la peau, les lèvre ou les fibres kératiniques.The subject of the invention is also the use of a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase as defined above, in a cosmetic composition comprising a cosmetically acceptable organic liquid medium, to obtain a deposit. , in particular make-up, non-transfer to keratin materials, in particular to the skin, the lips or the keratin fibers.
Le transfert du dépôt obtenu avec la composition selon l'invention est déterminé selon le protocole décrit ci-après.The transfer of the deposit obtained with the composition according to the invention is determined according to the protocol described below.
On préchauffe un support (rectangle de 40 mm X 70 mm et d'épaisseur 3 mm) de mousse de polyethylene adhésif sur une des faces ayant une densité de 33 kg/m3 (vendue sous la dénomination RE40X70EP3 de la société JOINT TECHNIQUE LYONNAIS IND) sur une plaque chauffante maintenue à la température de 40 °C pour que la surface du support soit maintenue à une température de 33 °C ± 1 °C.A support (rectangle of 40 mm X 70 mm and thickness 3 mm) of pre-heated polyethylene foam is preheated on one of the faces having a density of 33 kg / m3 (sold under the name RE40X70EP3 from the company JOINT TECHNIQUE LYONNAIS IND) on a hot plate maintained at a temperature of 40 ° C so that the surface of the support is maintained at a temperature of 33 ° C ± 1 ° C.
Tout en laissant le support sur la plaque chauffante, on applique la composition sur toute la surface non adhésive du support en l'étalant à l'aide d'un pinceau pour obtenir un dépôt de la composition d'environ 15 μm puis on laisse sécher pendant 30 minutes.While leaving the support on the hot plate, the composition is applied to the entire non-adhesive surface of the support, spreading it out using a brush to obtain a deposit of the composition of approximately 15 μm and then allowed to dry. during 30 minutes.
Après séchage, le support est collé par sa face adhésive sur une enclume d'un diamètre de 20 mm et munie d'un pas de vis. L'ensemble support dépôt est ensuite découpé à l'aide d'un emporte- pièce d'un diamètre de 18 mm. L'enclume est ensuite vissée sur une presse (STATIF MANUEL IMADA SV-2 de la société SOMECO) équipée d'un dynanomètre (IMADA DPS-20 de la société SOMECO).After drying, the support is glued by its adhesive side to an anvil with a diameter of 20 mm and provided with a thread. The deposit support assembly is then cut using a punch with a diameter of 18 mm. The anvil is then screwed onto a press (STATIF MANUEL IMADA SV-2 from SOMECO) equipped with a dynanometer (IMADA DPS-20 from SOMECO).
Un papier blanc pour photocopieuse de 80g/m2 est placé sur le socle de la presse puis on presse l'ensemble support/dépôt sur le papier à une pression de 2,5 kg pendant 30 secondes. Après retrait de l'ensemble support dépôt, une partie du dépôt a transféré sur le papier. On mesure alors la couleur du dépôt transféré sur le papier à l'aide d'un colorimètre MINOLTA CR300 , la couleur étant caractérisée par les paramètres colorimétriques L*, a*, b* . On détermine les paramètres colorimétriques L*n, a*n, b*o de la couleur du papier nu utilisé.A white photocopier paper of 80 g / m2 is placed on the base of the press and then the support / deposition assembly is pressed on the paper at a pressure of 2.5 kg for 30 seconds. After removal of the deposit support assembly, part of the deposit transferred to paper. The color of the deposit transferred to the paper is then measured using a MINOLTA CR300 colorimeter, the color being characterized by the parameters colorimetric L *, a *, b * . The color parameters L * n, a * n, b * o of the color of the bare paper used are determined.
On détermine alors la différence de couleur ΔE1 entre la couleur du dépôt transféré par rapport à la couleur du papier nu par la relation suivante.The color difference ΔE1 is then determined between the color of the transferred deposit relative to the color of the bare paper by the following relationship.
'(L*-L0*)2 + (a* - a0*)2 + (b* - b0*)°'(L * -L 0 *) 2 + (a * - a 0 *) 2 + (b * - b 0 *) °
ΔE1 =ΔE1 =
Par ailleurs, on prépare une référence de transfert total en appliquant la composition directement sur un papier identique à celui utilisé précédemment, à la température ambiante (25 °C), en étalant la composition à l'aide d'un pinceau et pour obtenir un dépôt de la composition d'environ 15 μm puis on laisse sécher pendant 30 minutes à la température ambiante (25 °C). Après séchage, on mesure directement les paramètres colorimétriques L*', a*', b*' de la couleur du dépôt mis sur le papier, correspondant à la couleur de référence de transfert total. On détermine les paramètres colorimétriques L*'o, a*'o, b*'o de la couleur du papier nu utilisé.Furthermore, a total transfer reference is prepared by applying the composition directly to a paper identical to that used previously, at room temperature (25 ° C), spreading the composition using a brush and to obtain a depositing the composition of about 15 μm and then allowing it to dry for 30 minutes at room temperature (25 ° C). After drying, the colorimetric parameters L * ', a *', b * 'of the color of the deposit placed on the paper, directly corresponding to the reference color of total transfer, are measured directly. The color parameters L * 'o, a *' o, b * 'o of the color of the bare paper used are determined.
On détermine alors la différence de couleur ΔE2 entre la couleur de référence de transfert total par rapport à la couleur du papier nu par la relation suivante.The color difference ΔE2 is then determined between the reference color of total transfer with respect to the color of the bare paper by the following relation.
ΔE2 '(L*'-L0 + (a*' - a0 **)2 + (b*' - b0 *')2 ΔE2 '(L *' - L 0 + (a * '- a 0 ** ) 2 + (b * ' - b 0 * ') 2
Le transfert de la composition, exprimé en pourcentage, est égal au rapportThe transfer of the composition, expressed as a percentage, is equal to the ratio
100 X ΔE1 / ΔE2 La mesure est effectuée sur 4 supports à la suite et la valeur de transfert correspond à la moyenne des 4 mesures obtenues avec les 4 supports.100 X ΔE1 / ΔE2 The measurement is carried out on 4 supports in succession and the transfer value corresponds to the average of the 4 measurements obtained with the 4 supports.
La composition selon l'invention comprend une dispersion de particules de polymère éthylenique greffé non siliconé.The composition according to the invention comprises a dispersion of particles of non-silicone grafted ethylenic polymer.
Par polymère "éthylenique" , on entend un polymère obtenu par polymérisation de monomères comprenant une insaturation éthylenique.By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
Par polymère greffé non siliconé, on entend un polymère greffé contenant majoritairement un macromonomère carboné et contenant éventuellement au plus 7 % en poids, de préférence au plus 5 % en poids, voire est exempt de macromonomère siliconé. La dispersion de polymère éthylenique greffé non siliconé est notamment exempte de polymère stabilisant distinct dudit polymère greffé, tels que ceux décrits dans EP749747, et les particules de polymère éthylenique greffé ne sont donc pas stabilisées en surface par de tels polymères stabilisants additionnels. Le polymère greffé est donc dispersé dans la phase grasse liquide en l'absence de stabilisant additionnel en surface des particules.The term “non-silicone graft polymer” means a graft polymer mainly containing a carbon macromonomer and optionally containing at most 7% by weight, preferably at most 5% by weight, or even is free of silicone macromonomer. The dispersion of non-silicone grafted ethylenic polymer is in particular free of stabilizing polymer distinct from said grafted polymer, such as those described in EP749747, and the particles of grafted ethylenic polymer are therefore not surface stabilized by such additional stabilizing polymers. The grafted polymer is therefore dispersed in the liquid fatty phase in the absence of additional stabilizer at the surface of the particles.
Par polymère greffé, on entend un polymère ayant un squelette comprenant au moins une chaîne latérale pendante ou située en bout de chaîne, et de préférence pendante.The term “grafted polymer” is intended to mean a polymer having a backbone comprising at least one side chain hanging or situated at the end of the chain, and preferably hanging.
Avantageusement, le polymère éthylenique greffé non siliconé comprend un squelette éthylenique insoluble dans ladite phase grasse liquide, et des chaînes latérales liées de manière covalente audit squelette et solubles dans la phase grasse liquide. Le polymère éthylenique greffé non siliconé est notamment un polymère non réticulé. En particulier, le polymère est obtenu par polymérisation de monomères comprenant un seul groupement polymérisable.Advantageously, the non-silicone grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase, and side chains covalently linked to said skeleton and soluble in the liquid fatty phase. The non-silicone grafted ethylenic polymer is in particular a non-crosslinked polymer. In particular, the polymer is obtained by polymerization of monomers comprising a single polymerizable group.
De préférence, le polymère éthylenique greffé non siliconé est un polymère filmogène. Par polymère "filmogène", on entend un polymère apte à former à lui seul ou en présence d'un agent auxiliaire de filmification, un film continu, notamment à l'œil et au toucher, et adhérent sur un support, notamment sur les matières kératiniques.Preferably, the non-silicone grafted ethylenic polymer is a film-forming polymer. By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous film, in particular to the eye and to the touch, and adherent on a support, in particular on materials. keratin.
Selon un mode de réalisation de l'invention, le polymère éthylenique greffé est un polymère acrylique greffé.According to one embodiment of the invention, the grafted ethylenic polymer is a grafted acrylic polymer.
Le polymère éthylenique greffé non siliconé est notamment susceptible d'être obtenu par polymérisation radicalaire dans un milieu organique de polymérisation :The non-silicone grafted ethylenic polymer is in particular capable of being obtained by radical polymerization in an organic polymerization medium:
- d'au moins un monomère éthylenique, en particulier d'au moins un monomère acrylique et éventuellement d'au moins un monomère additionnel vinylique non acrylique, pour former ledit squelette insoluble ; et- At least one ethylenic monomer, in particular at least one acrylic monomer and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble skeleton; and
- d'au moins un macromonomère comportant un groupe terminal polymérisable pour former les chaînes latérales, ledit macromonomère ayant une masse moléculaire moyenne en poids supérieure ou égale à 200 et la teneur en macromonomère polymérisé représentant de 0,05 à 20 % en poids du polymère.- At least one macromonomer comprising a polymerizable end group to form the side chains, said macromonomer having a weight average molecular weight greater than or equal to 200 and the content of polymerized macromonomer representing from 0.05 to 20% by weight of the polymer .
La phase grasse liquide peut contenir le milieu organique de polymérisation.The liquid fatty phase may contain the organic polymerization medium.
Le milieu organique liquide de dispersion, correspondant au milieu dans lequel est fourni le polymère greffé, peut être identique au milieu de polymérisation. Toutefois, le milieu de polymérisation peut être substitué en tout ou partie par un autre milieu organique liquide. Cet autre milieu organique liquide peut être ajouté, après polymérisation, au milieu de polymérisation. Ce dernier est ensuite évaporé en tout ou partie.The liquid organic dispersion medium, corresponding to the medium in which the grafted polymer is supplied, may be identical to the polymerization medium. However, the polymerization medium can be substituted in whole or in part by another liquid organic medium. This other liquid organic medium can be added, after polymerization, to the polymerization medium. The latter is then evaporated in whole or in part.
La phase grasse liquide peut contenir des composés liquides organiques autres que ceux présents dans le milieu de dispersion. Ces autres composés sont choisis de manière à ce que le polymère greffé reste à l'état de dispersion dans la phase grasse liquide.The liquid fatty phase can contain organic liquid compounds other than those present in the dispersion medium. These other compounds are chosen so that the grafted polymer remains in the state of dispersion in the liquid fatty phase.
Le milieu liquide organique de dispersion est présent dans la phase grasse liquide de la composition selon l'invention du fait de l'introduction dans la composition de la dispersion de polymère greffé obtenue.The organic liquid dispersion medium is present in the liquid fatty phase of the composition according to the invention due to the introduction into the composition of the graft polymer dispersion obtained.
La phase grasse liquide :The liquid fatty phase:
La phase grasse liquide comprend, de préférence majoritairement un ou plusieurs composés organiques liquides (ou huiles) tels que définis ci-après. En particulier, la phase grasse liquide est une phase organique liquide non aqueuse et non miscible à l'eau à la température ambiante (25 °C).The liquid fatty phase preferably comprises one or more liquid organic compounds (or oils) as defined below. In particular, the liquid fatty phase is a non-aqueous liquid organic phase which is immiscible with water at room temperature (25 ° C).
On entend par "composé organique liquide" un composé non aqueux qui est à l'état liquide à la température ambiante (25 °C) et qui s'écoule donc de son propre poids.The term “liquid organic compound” is understood to mean a non-aqueous compound which is in the liquid state at room temperature (25 ° C.) and which therefore flows from its own weight.
On entend par "composé siliconé" un composé contenant au moins un atome de silicium.The term “silicone compound” means a compound containing at least one silicon atom.
La composition selon l'invention contient avantageusement une huile volatile telleThe composition according to the invention advantageously contains a volatile oil such
que décrite ci-après. Par huile volatile, on entend une huile susceptible de s'évaporer de la peau ouas described below. By volatile oil is meant an oil capable of evaporating from the skin or
des lèvres en moins d'une heure, ayant notamment une pression de vapeur, àlips in less than an hour, having in particular a vapor pressure,
température ambiante et pression atmosphérique allant de 10"3 à 300 mm de Hg (0,13 Pa à 40 000 Pa).ambient temperature and atmospheric pressure ranging from 10 "3 to 300 mm Hg (0.13 Pa to 40,000 Pa).
L'huile volatile peut être siliconée ou non siliconée. Elle peut être notammentThe volatile oil can be silicone or non-silicone. It can be in particular
choisie parmi l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasiloxane, lechosen from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodécaméthylcyclohexasiloxane, l'heptaméthyl-hexyltrisiloxane, l'heptaméthyloctyltrisiloxane, Poctaméthyltrisiloxane, le décaméthyltétrasiloxane,dodecamethylcyclohexasiloxane, heptamethyl-hexyltrisiloxane, heptamethyloctyltrisiloxane, Poctamethyltrisiloxane, decamethyltetrasiloxane,
l'isododécane, l'isodécane, l'isohexadécane, et leurs mélanges. L'huile volatile est avantageusement présente en une teneur allant de 1 % à 70 % en poids, par rapport au poids total de la composition, de préférence allant de 5 % à 50 % en poids, et préférentiellement allant de 10 % à 35 % en poids.isododecane, isodecane, isohexadecane, and mixtures thereof. The volatile oil is advantageously present in a content ranging from 1% to 70% by weight, relative to the total weight of the composition, preferably ranging from 5% to 50% by weight, and preferably ranging from 10% to 35% in weight.
La phase grasse liquide peut contenir une huile non volatile telle que décrite ci- après. L'huile non volatile est avantageusement présente en une teneur allant de 1 % à 80 % en poids, par rapport au poids total de la composition, de préférence allant de 5 % à 60 % en poids, et préférentiellement allant de 10 % à 50 % en poids.The liquid fatty phase may contain a non-volatile oil as described below. The non-volatile oil is advantageously present in a content ranging from 1% to 80% by weight, relative to the total weight of the composition, preferably ranging from 5% to 60% by weight, and preferably ranging from 10% to 50 % in weight.
Parmi les composés organiques liquides ou huiles pouvant être présents dans le milieu organique liquide de dispersion, on peut citer :Among the liquid organic compounds or oils which may be present in the liquid organic dispersion medium, there may be mentioned:
- les composés organiques liquides, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2, de préférence inférieur ou égal à 17 (MPa)1/2,- liquid organic compounds, in particular non-silicone or silicone compounds, having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1/2 , preferably less than or equal to 17 (MPa) 1 / 2 ,
- les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 ; et- monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2 ; and
- leurs mélanges. Le paramètre de solubilité global δ selon l'espace de solubilité de Hansen est défini dans l'article « Solubility parameter values » de Eric A.Grulke de l'ouvrage « Polymer Handbook », 3éme édition, Chapitre VII, p.519-559 par la relation : δ= (dD 2 + dp2 + dH 2)1 2 dans laquelle- their mixtures. The global solubility parameter δ according to Hansen's solubility space is defined in the article “Solubility parameter values” by Eric A. Grulke of the book “Polymer Handbook”, 3 rd edition, Chapter VII, p.519- 559 by the relation: δ = (d D 2 + dp 2 + d H 2 ) 1 2 in which
- dD caractérise les forces de dispersion de LONDON issues de la formation de dipôles induits lors des chocs moléculaires,- d D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks,
- dp caractérise les forces d'interactions de DEBYE entre dipôles permanents, et - dH caractérise les forces d'interactions spécifiques (type liaisons hydrogène, acide/base, donneur/accepteur, etc.).- dp characterizes the DEBYE interaction forces between permanent dipoles, and - d H characterizes the specific interaction forces (such as hydrogen bonds, acid / base, donor / acceptor, etc.).
La définition des solvants dans l'espace de solubilité selon Hansen est décrite dans l'article de CM. Hansen « The three dimensional solubility parameters » J.Paint Technol. 39, 105 (1967).The definition of solvents in the solubility space according to Hansen is described in the article by CM. Hansen "The three dimensional solubility parameters" J.Paint Technol. 39, 105 (1967).
Parmi les composés liquides organiques, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (Mpa)1/2, on peut citer des corps gras liquides, notamment des huiles, qui peuvent être choisis parmi les huiles naturelles ou synthétiques, carbonées, hydrocarbonées, fluorées, siliconées, éventuellement ramifiées, seules ou en mélange.Among the organic liquid compounds, in particular non-silicone or silicone compounds, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 (Mpa) 1/2 , liquid fatty substances, in particular oils, may be mentioned which can be chosen from natural or synthetic, carbon, hydrocarbon, fluorinated, silicone oils, optionally branched, alone or as a mixture.
Parmi ces huiles, on peut citer les huiles végétales formées par des esters d'acides gras et de polyols, en particulier les triglycérides, telles que l'huile de tournesol, de sésame ou de colza, ou les esters dérivés d'acides ou d'alcools à longue chaîne (c'est-à-dire ayant de 6 à 20 atomes de carbone), notamment les esters de formule RCOOR' dans laquelle R représente le reste d'un acide gras supérieur comportant de 7 à 19 atomes de carbone et R' représente une chaîne hydrocarbonée comportant de 3 à 20 atomes de carbone, tels que les palmitates, les adipates et les benzoates, notamment l'adipate de diisopropyle.Among these oils, mention may be made of vegetable oils formed by esters of fatty acids and of polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or d 'long chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R 'represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular adipate of diisopropyl.
On peut également citer les alcanes linéaires, ramifiés et/ou cycliques éventuellement volatils et notamment des huiles de paraffine, de vaseline, ou le polyisobutylène hydrogéné, l'isododécane, ou encore les 'ISOPARS', les isoparaffines volatiles. On peut citer également les esters, les éthers, les cétones.Mention may also be made of linear, branched and / or cyclic alkanes which may be volatile and in particular paraffin oils, of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones.
On peut encore citer les huiles siliconées telles que les polydiméthylsiloxanes et les polyméthylphénylsiloxanes, éventuellement substitués par des groupements aliphatiques et/ou aromatiques, éventuellement fluorés, ou par des groupements fonctionnels tels que des groupements hydroxyles, thiols et/ou aminés, et les huiles siliconées volatiles, notamment cycliques.Mention may also be made of silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups, and silicone oils volatile, especially cyclical.
En particulier, on peut citer les huiles de silicone, éventuellement ramifiées, volatiles et/ou non volatiles.In particular, mention may be made of silicone oils, optionally branched, volatile and / or non-volatile.
Par huile volatile, on entend une huile susceptible de s'évaporer de la peau ou des lèvres en moins d'une heure, ayant notamment une pression de vapeur, à température ambiante et pression atmosphérique allant de 10"3 à 300 mm de Hg (0,13 Pa à 40 000 Pa). Comme huile siliconée volatile utilisable dans l'invention, on peut citer les siliconés linéaires ou cycliques ayant de 2 à 7 atomes de silicium, ces siliconés comportant éventuellement des groupes alkyle ou alkoxy ayant de 1 à 10 atomes de carbone. En particulier, on peut citer l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasiloxane, le dodécaméthylcyclohexasiloxane, l'heptaméthylhexyltrisiloxane, l'heptaméthyloctyltrisiloxane, l'octaméthyltrisiloxane, le décaméthyltétrasiloxane et leurs mélanges.By volatile oil is meant an oil capable of evaporating from the skin or the lips in less than an hour, having in particular a vapor pressure, at ambient temperature and atmospheric pressure ranging from 10 −3 to 300 mm of Hg ( 0.13 Pa to 40,000 Pa) As volatile silicone oil which can be used in the invention, mention may be made of linear or cyclic silicones having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, in particular, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane and decamethyltetrasil can be mentioned.
Comme huile siliconée non volatile, on peut citer les polydialkylsiloxanes non volatils, tels que les polydiméthylsiloxanes (PDMS) non volatils; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone; les siliconés phénylées comme les phényl triméthicones, les phényl diméthicones, les phényl triméthylsiloxy diphénylsiloxanes, les diphényl diméthicones, les diphényl méthyldiphényl trisiloxanes, les polyméthylphénylsiloxanes; les polysiloxanes modifiés par des acides gras (notamment en C8-C2θ)> des alcools gras (notamment en Cg-C2θ) °u des polyoxyalkylènesAs non-volatile silicone oil, there may be mentioned non-volatile polydialkylsiloxanes, such as non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, polymethylphenylsiloxanes; polysiloxanes modified with fatty acids (especially C8-C2θ) > fatty alcohols (especially Cg-C2θ) ° u polyoxyalkylenes
(notamment polyoxyéthyléne et/ou polyoxypropylène); les polysiloxanes aminées ; les polysiloxanes à groupement hydroxyles; les polysiloxanes fluorés comportant un groupement fluoré pendant ou en bout de chaîne siliconée ayant de 1 à 12 atomes de carbone dont tout ou partie des hydrogène sont substitués par des atomes de fluor ; et leurs mélanges.(in particular polyoxyethylene and / or polyoxypropylene); amino polysiloxanes; polysiloxanes containing hydroxyl groups; fluorinated polysiloxanes comprising a fluorinated group during or at the end of the silicone chain having from 1 to 12 carbon atoms of which all or part of the hydrogen are substituted by fluorine atoms; and their mixtures.
On peut citer, en particulier, comme composés organiques liquides non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (Mpa)1/2 :Mention may be made, in particular, as non-silicone liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (Mpa) 1/2 :
- les esters linéaires, ramifiés ou cycliques, ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone;- linear, branched or cyclic esters, having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms;
- les éthers ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone ; et- ethers having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms; and
- les cétones ayant au moins 6 atomes de carbone, notamment de 6 à 30 atomes de carbone.- ketones having at least 6 carbon atoms, in particular from 6 to 30 carbon atoms.
Par monoalcools liquides ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2, on entend les monoalcools liquides gras aliphatiques ayant de 6 à 30 atomes de carbone, la chaîne hydrocarbonée ne comportant pas de groupement de substitution. Comme monoalcools selon l'invention, on peut citer l'alcool oléique, le décanol, l'octyldodécanol et l'alcool linoléique.By liquid monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , is meant aliphatic fatty liquid monoalcohols having from 6 to 30 carbon atoms, the hydrocarbon chain not comprising no substitution group. As monoalcohols according to the invention, there may be mentioned oleic alcohol, decanol, octyldodecanol and linoleic alcohol.
Milieu non siliconé Selon un premier mode de réalisation de l'invention, la phase grasse liquide peut être une phase grasse liquide non siliconée.Non-silicone medium According to a first embodiment of the invention, the liquid fatty phase can be a non-silicone liquid fatty phase.
On entend par "phase grasse liquide non siliconée" une phase grasse comprenant un ou plusieurs composés organiques liquides ou huiles non siliconé(e)s, tels que ceux cités précédemment, lesdits composés non siliconés étant présents majoritairement dans la phase grasse liquide, c'est-à-dire à au moins 50 % en poids, notamment de 50 à 100 % en poids, de préférence de 60 % à 100 % en poids (par exemple de 60 à 99 % en poids), ou encore de 65 % à 100 % en poids (par exemple de 65 à 95 % en poids), par rapport au poids total de la phase grasse liquide.The term “non-silicone liquid fatty phase” means a fatty phase comprising one or more liquid organic compounds or non-silicone oils, such as those mentioned above, said non-silicone compounds being present mainly in the liquid fatty phase, it that is to say at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or even from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
Les composés organiques liquides non siliconés peuvent être notamment choisis parmi :The non-silicone-based liquid organic compounds can in particular be chosen from:
- les composés organiques liquides non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1 2,non-silicone-based liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2 ,
- les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 ; et- monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2 ; and
- leurs mélanges.- their mixtures.
Ladite phase grasse liquide non siliconée peut donc éventuellement comprendre des composés organiques liquide ou huiles siliconé(e)s, tels que ceux cités précédemment, qui peuvent être présents en une quantité inférieure à 50 % en poids, notamment allant de 0,1 à 40 % en poids, voire allant de 1 à 35 % en poids, ou encore allant de 5 à 30 % en poids, par rapport au poids total de la phase grasse liquide.Said non-silicone-based liquid fatty phase may therefore optionally comprise liquid organic compounds or silicone oils, such as those mentioned above, which may be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40 % by weight, or even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
Selon un mode particulier de réalisation de l'invention, la phase grasse liquide non siliconée ne contient pas de composés organiques liquides ou huiles siliconé(e)s.According to a particular embodiment of the invention, the non-silicone liquid fatty phase does not contain liquid organic compounds or silicone oils.
Lorsque la phase grasse liquide est une phase grasse liquide non siliconée, les macromonères présents dans le polymère greffé sont avantageusement des macromonomères carbonés tels que décrits ci-après.When the liquid fatty phase is a non-silicone liquid fatty phase, the macromoners present in the grafted polymer are advantageously carbon macromonomers as described below.
Milieu siliconé :Silicone medium:
Selon un deuxième mode de réalisation de l'invention, la phase grasse liquide peut être une phase grasse liquide siliconée.According to a second embodiment of the invention, the liquid fatty phase can be a silicone liquid fatty phase.
On entend par "phase grasse liquide siliconée" une phase grasse comprenant un ou plusieurs composés organiques liquides siliconés ou huiles siliconées tels que ceux décrits précédemment, lesdits composés siliconés étant présents majoritairement dans la phase grasse liquide, c'est-à-dire à au moins 50 % en poids, notamment de 50 à 100 % en poids, de préférence de 60 % à 100 % en poids (par exemple de 60 à 99 % en poids), ou encore de 65 % à 100 % en poids (par exemple de 65 à 95 % en poids), par rapport au poids total de la phase grasse liquide.The term “silicone liquid fatty phase” means a fatty phase comprising one or more silicone liquid organic compounds or silicone oils such as those described above, said silicone compounds being present mainly in the liquid fatty phase, that is to say at least at least 50% by weight, in particular from 50 to 100% by weight, preferably from 60% to 100% by weight (for example from 60 to 99% by weight), or also from 65% to 100% by weight (for example from 65 to 95% by weight), relative to the total weight of the liquid fatty phase.
Les composés organiques liquides siliconés peuvent être notamment choisis parmi : - les composés organiques liquides, notamment non siliconés ou siliconés, ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1 2.The liquid organic silicone compounds can be chosen in particular from: - liquid organic compounds, in particular non-silicone or silicone, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2 .
Ladite phase grasse liquide siliconée peut donc éventuellement comprendre des composés organiques liquides ou huiles non siliconé(e)s, tels que décrits précédemment, qui peuvent être présents en une quantité inférieure à 50 % en poids, notamment allant de 0,1 à 40 % en poids, voire allant de 1 à 35 % en poids, ou encore allant de 5 à 30 % en poids, par rapport au poids total da la phase grasse liquide.Said liquid silicone fatty phase can therefore optionally comprise liquid organic compounds or non-silicone oils, as described above, which can be present in an amount of less than 50% by weight, in particular ranging from 0.1 to 40% by weight, even ranging from 1 to 35% by weight, or even ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase.
Selon un mode particulier de réalisation de l'invention, la phase grasse liquide siliconée ne contient pas de composés organiques liquides non siliconés.According to a particular embodiment of the invention, the liquid silicone fatty phase does not contain non-silicone liquid organic compounds.
Le polymère greffe :The polymer grafts:
Le choix des monomères constituant le squelette du polymère, des macromonomères, le poids moléculaire du polymère, la proportion des monomères et des macromonomères peut être fait en fonction du milieu organique liquide de dispersion de manière à obtenir avantageusement une dispersion de particules de polymères greffés en particulier une dispersion stable, ce choix pouvant être effectué par l'homme du métier.The choice of monomers constituting the backbone of the polymer, of the macromonomers, the molecular weight of the polymer, the proportion of the monomers and of the macromonomers can be made as a function of the liquid organic dispersion medium so as to advantageously obtain a dispersion of polymer particles grafted in particularly a stable dispersion, this choice can be made by a person skilled in the art.
Par "dispersion stable", on entend une dispersion qui n'est pas susceptible de former de dépôt solide ou de déphasage liquide/solide notamment après une centrifugation, par exemple, à 4000 tours/minute pendant 15 minutes.By "stable dispersion" is meant a dispersion which is not liable to form a solid deposit or a liquid / solid phase shift, in particular after centrifugation, for example, at 4000 rpm for 15 minutes.
Le polymère éthylenique greffé non siliconé formant les particules en dispersion comprend donc un squelette insoluble dans ledit milieu de dispersion et une partie soluble dans ledit milieu de dispersion.The non-silicone grafted ethylenic polymer forming the particles in dispersion therefore comprises a skeleton insoluble in said dispersion medium and a part soluble in said dispersion medium.
Le polymère éthylenique greffé peut être un polymère statistique.The grafted ethylenic polymer can be a random polymer.
Selon l'invention, on entend par "polymère éthylenique greffé " un polymère susceptible d'être obtenu par polymérisation radicalaire :According to the invention, the term “grafted ethylenic polymer” means a polymer capable of being obtained by radical polymerization:
- d'un ou plusieurs monomère(s) éthylénique(s),- one or more ethylenic monomer (s),
- avec un ou plusieurs macromonomère(s), dans un milieu organique de polymérisation.- with one or more macromonomer (s), in an organic polymerization medium.
Selon l'invention, on entend par "polymère acrylique greffé " un polymère susceptible d'être obtenu par polymérisation radicalaire : - d'un ou plusieurs monomère(s) acrylique(s), et éventuellement d'un ou plusieurs monomère(s) additionnel(s) vinylique(s) non acrylique(s),According to the invention, the term “grafted acrylic polymer” means a polymer capable of being obtained by radical polymerization: - one or more acrylic monomer (s), and optionally one or more additional non-acrylic vinyl monomer (s),
- avec un ou plusieurs macromonomère(s), dans un milieu organique de polymérisation.- with one or more macromonomer (s), in an organic polymerization medium.
Avantageusement, les monomères acryliques représentent de 50 à 100 % en poids, de préférence de 55 à 100 % en poids (notamment de 55 à 95 % en poids), préférentiellement de 60 à 100 % en poids (notamment de 60 à 90 % en poids) du mélange monomères acryliques + monomères vinyliques non acryliques éventuels.Advantageously, the acrylic monomers represent from 50 to 100% by weight, preferably from 55 to 100% by weight (especially from 55 to 95% by weight), preferably from 60 to 100% by weight (especially from 60 to 90% by weight). weight) of the mixture of acrylic monomers + optional non-acrylic vinyl monomers.
De préférence, les monomères acryliques sont choisis parmi les monomères dont l'homopolymère est insoluble dans le milieu de dispersion considéré, c'est-à-dire que l'homopolymère est sous forme solide (ou non dissous) à une concentration supérieure ou égale à 5% en poids à température ambiante (20°C) dans ledit milieu de dispersion.Preferably, the acrylic monomers are chosen from monomers whose homopolymer is insoluble in the dispersion medium under consideration, that is to say that the homopolymer is in solid form (or not dissolved) at a greater or equal concentration. at 5% by weight at room temperature (20 ° C) in said dispersion medium.
Macromonomères :Macromonomers:
Selon l'invention, on entend par "macromonomère ayant un groupe terminal polymérisable" tout polymère comportant sur une seule de ses extrémités un groupe terminal polymérisable apte à réagir lors de la réaction de polymérisation avec les monomères acryliques et éventuellement les monomères vinyliques non acryliques additionnels constituant le squelette. Le macromonomère permet de former les chaînes latérales du polymère acrylique greffé. Le groupe polymérisable du macromonomère peut être avantageusement un groupe à insaturation éthylenique susceptible de se polymériser par voie radicalaire avec les monomères constituant le squelette.According to the invention, the term "macromonomer having a polymerizable end group" means any polymer comprising on only one of its ends a polymerizable end group capable of reacting during the polymerization reaction with acrylic monomers and optionally additional non-acrylic vinyl monomers constituting the skeleton. The macromonomer makes it possible to form the side chains of the grafted acrylic polymer. The polymerizable group of the macromonomer can advantageously be an ethylenically unsaturated group capable of polymerizing by the radical route with the monomers constituting the skeleton.
Le macromère est un macromère carboné. Par "macromonomère carboné" on entend un macromonomère non siliconé, et notamment un macromonomère oligomère obtenu par polymérisation de monomère(s) non siliconé(s) à insaturation éthylenique, et principalement par polymérisation de monomères acryliques et/ou vinyliques non acryliques.The macromer is a carbon macromer. By "carbon macromonomer" is meant a non-silicone macromonomer, and in particular an oligomeric macromonomer obtained by polymerization of non-silicone monomer (s) with ethylenic unsaturation, and mainly by polymerization of acrylic and / or non-acrylic vinyl monomers.
Par "macromonomère siliconé" on entend un macromonomère organopolysiloxane, et en particulier un macromonomère polydiméthylsiloxane.By "silicone macromonomer" is meant an organopolysiloxane macromonomer, and in particular a polydimethylsiloxane macromonomer.
De préférence, le macromonomère est choisi parmi les macromonomères dont l'homopolymère est soluble dans le milieu de dispersion considéré, c'est-à-dire complètement dissous à une concentration supérieure ou égale à 5 % en poids et à température ambiante dans ledit milieu de dispersion.Preferably, the macromonomer is chosen from macromonomers whose homopolymer is soluble in the dispersion medium under consideration, that is to say completely dissolved at a concentration greater than or equal to 5% by weight and at room temperature in said medium of dispersion.
Ainsi, le polymère acrylique greffé comprend un squelette (ou chaîne principale) constitué par un enchaînement de motifs acryliques résultant de la polymérisation notamment d'un ou plusieurs monomères acryliques et des chaînes latérales (ou greffons) issus de la réaction des macromonomères, lesdites chaînes latérales étant liées de manière covalente à ladite chaîne principale.Thus, the grafted acrylic polymer comprises a skeleton (or main chain) consisting of a chain of acrylic units resulting from the polymerization in particular of one or more acrylic monomers and side chains (or grafts) resulting from the reaction of the macromonomers, said chains side being covalently linked to said main chain.
Le squelette (ou chaîne principale) est insoluble dans le milieu de dispersionconsidéré alors que les chaînes latérales (ou greffons) sont solubles dans ledit milieu de dispersion.The skeleton (or main chain) is insoluble in the dispersion medium considered while the side chains (or grafts) are soluble in said dispersion medium.
Les monomères :The monomers:
Par "monomère acryliques", on entend dans la présente demande des monomères choisis parmi l'acide (méth)acrylique, les esters de l'acide (méth)acrylique (appelés également les (méth)acrylates), les amides de l'acide (méthacrylique) (appelés également les (méth)acrylamides). Comme monomère acrylique susceptible d'être employé pour former le squelette insoluble du polymère, on peut citer, seul ou en mélange, les monomères suivants, ainsi que leurs sels :By "acrylic monomer" is meant in the present application monomers chosen from (meth) acrylic acid, esters of (meth) acrylic acid (also called (meth) acrylates), acid amides (methacrylic) (also called (meth) acrylamides). As acrylic monomer capable of being used to form the insoluble backbone of the polymer, mention may be made, alone or as a mixture, of the following monomers, as well as their salts:
-(i) les (méth)acrylates de formule :- (i) (meth) acrylates of formula:
CH2 C COOR2 CH 2 C COOR 2
Ri dans laquelle : - R1 désigne un atome d'hydrogène ou un groupe méthyle ; - R2 représente un groupe choisi parmi :Ri in which: - R 1 denotes a hydrogen atom or a methyl group; - R 2 represents a group chosen from:
- un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S; et/ou pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C1-C4; et/ou pouvant être substitué par au moins un groupe polyoxyalkylène, en particulier avec alkylène en C2-C4, notamment polyoxyéthylène et/ou polyoxypropylène, ledit groupe polyoxyalkylène étant constitué par la répétition de 5 à 30 motifs oxyalkylène; - un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S, et ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I);- a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in C1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular with C2-C4 alkylene, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units; a cyclic alkyl group comprising from 3 to 6 carbon atoms, the said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and or possibly comprising one or more substituents chosen from OH and the halogen atoms (F, Cl, Br, I);
A titre d'exemples de R2, on peut citer le groupe méthyle, éthyle, propyle, butyle, isobutyle, méthoxyéthyle, éthoxyéthyle, méthoxy-polyoxyéthylène 350 OE , trifluoroéthyle, 2-hydroxyéthyle, 2-hydroxypropyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle.As examples of R 2 , mention may be made of the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene 350 EO, trifluoroethyl, group. 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
-(ii) les (méth)acrylamides de formule :- (ii) the (meth) acrylamides of formula:
Figure imgf000021_0001
dans laquelle :
Figure imgf000021_0001
in which :
- R3 désigne un atome d'hydrogène ou un groupe méthyle ;- R 3 denotes a hydrogen atom or a methyl group;
- R et R5, identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle, linéaire ou ramifié, comportant de 1 à 6 atomes de carbone, pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en- R and R 5 , identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in
- R4 représente un atome d'hydrogène et R5 représente un groupe 1,1-diméthyl-3- oxobutyle.- R 4 represents a hydrogen atom and R 5 represents a 1,1-dimethyl-3-oxobutyl group.
A titre d'exemples de groupes alkyles pouvant constituer R et R5, on peut citer n-butyle, t-butyle, n-propyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle.As examples of alkyl groups which may constitute R and R 5 , there may be mentioned n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
-(iii) les monomères (méth)acryliques comprenant au moins une fonction acide carboxylique, phosphorique ou sulfonique, tels que l'acide acrylique, l'acide méthacrylique, l'acide acrylamidopropanesulfonique.- (iii) (meth) acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid.
Parmi ces monomères acryliques, on peut tout particulièrement citer les (méth)acrylates de méthyle, d'éthyle, de propyle, de butyle, d'isobutyle; les (méth)acrylates de méthoxyéthyle ou d'éthoxyéthyle; le méthacrylate de trifluoroéthyle; le méthacrylate de diméthylaminoéthyle, le méthacrylate de diéthylaminoéthyle, le méthacrylate de 2- hydroxypropyle, le méthacrylate de 2-hydroxyéthyle, l'acrylate de 2-hydroxypropyle, l'acrylate de 2-hydroxyéthyle ; le diméthylaminopropylméthacrylamide; et leurs sels ; et leurs mélanges.Among these acrylic monomers, mention may very particularly be made of methyl, ethyl, propyl, butyl and isobutyl (meth) acrylates; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2- methacrylate hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide; and their salts; and their mixtures.
De préférence, les monomères acryliques sont choisis parmi l'acrylate de méthyle, l'acrylate de méthoxyéthyle, le méthacrylate de méthyle, le méthacrylate de 2- hydroxyéthyle, l'acide (meth)acrylique, le méthacrylate de diméthylaminoéthyle, et leurs mélanges.Preferably, the acrylic monomers are chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, (meth) acrylic acid, dimethylaminoethyl methacrylate, and their mixtures.
Parmi les monomères additionnels vinyliques non acryliques, on peut citer : - les esters vinylique de formule : R6-COO-CH=CH2 dans laquelle R6 représente un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes, ou un groupe alkyle cyclique comportant de 3 à 6 atomes de carbone et/ou un groupe aromatique, par exemple de type benzénique, anthracénique, et naphtalénique ;Among the additional non-acrylic vinyl monomers, there may be mentioned: - vinyl esters of formula: R 6 -COO-CH = CH 2 in which R 6 represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or a group cyclic alkyl comprising from 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene and naphthalene type;
- les monomères vinyliques non acryliques comprenant au moins une fonction acide carboxylique, phosphorique ou sulfonique, tels que l'acide crotonique, l'anhydride maléique, l'acide itaconique, l'acide fumarique, l'acide maléique, l'acide styrènesulfonique, l'acide vinylbenzoïque, l'acide vinylphosphorique, et leurs sels ;non-acrylic vinyl monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, and their salts;
- les monomères vinyliques non acryliques comprenant au moins une fonction aminé tertiaire, tels que la 2-vinylpyridine, la 4-vinylpyridine ; - et leurs mélanges.- non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine; - and their mixtures.
Avantageusement, les monomères acryliques présents dans le polymère greffésAdvantageously, the acrylic monomers present in the grafted polymer
comprennent au moins l'acide (méth)acrylique et au moins un monomère choisiinclude at least (meth) acrylic acid and at least one selected monomer
parmi les (méth)acrylates et les (méth)acrylamides décrits précédemment auxamong the (meth) acrylates and (meth) acrylamides described above in
points (i) et (ii). De préférence, les monomères acryliques comprennent au moinspoints (i) and (ii). Preferably, the acrylic monomers comprise at least
l'acide (méth)acrylique et au moins un monomère choisi parmi les (méth)acrylates(meth) acrylic acid and at least one monomer chosen from (meth) acrylates
d'alkyle en C1-C3. L'acide (méth)acrylique peut être présent en une teneur d'au moins 5 % en poids, par rapport au poids total du polymère, notamment allant deC1-C3 alkyl. The (meth) acrylic acid may be present in a content of at least at least 5% by weight, relative to the total weight of the polymer, in particular ranging from
5 % à 80 % en poids, de préférence d'au moins 10 % en poids, notamment allant5% to 80% by weight, preferably at least 10% by weight, in particular ranging
de 10 % en poids à 70 % en poids, préférentiellement d'au moins 15 % en poids,from 10% by weight to 70% by weight, preferably at least 15% by weight,
notamment allant de 15 % à 60 % en poids.in particular ranging from 15% to 60% by weight.
Parmi les sels, on peut citer ceux obtenus par neutralisation des groupements acides à l'aide de base inorganiques telles que l'hydroxyde de sodium, l'hydroxyde de potassium, l'hydroxyde d'ammonium ou de bases organiques de type alkanols aminés comme la monoéthanolamine, la diéthanolamine, la triéthanolamine, la 2-méthyl-2-amino-1 - propanol.Among the salts, there may be mentioned those obtained by neutralization of the acid groups using inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or organic bases of amino alkanol type such as monoethanolamine, diethanolamine, triethanolamine, 2-methyl-2-amino-1-propanol.
On peut également citer les sels formés par neutralisation des motifs aminé tertiaire, par exemple à l'aide d'acide minéral ou organique. Parmi les acides minéraux, on peut citer l'acide sulfurique ou l'acide chlorhydrique, l'acide bromhydrique, iodhydrique, l'acide phosphorique, l'acide borique. Parmi les acides organiques, on peut citer les acides comportant un ou plusieurs groupes carboxylique, sulfonique, ou phosphonique. Il peut s'agir d'acides aliphatiques linéaires, ramifiés ou cycliques ou encore d'acides aromatiques. Ces acides peuvent comporter, en outre, un ou plusieurs hétéroatomes choisis parmi O et N, par exemple sous la forme de groupes hydroxyles. On peut notamment citer l'acide acétique ou l'acide propionique, l'acide téréphtalique, ainsi que l'acide citrique et l'acide tartrique.Mention may also be made of the salts formed by neutralization of the tertiary amine units, for example using mineral or organic acid. Among the mineral acids, there may be mentioned sulfuric acid or hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid. Among the organic acids, mention may be made of acids comprising one or more carboxylic, sulphonic or phosphonic groups. They can be linear, branched or cyclic aliphatic acids or even aromatic acids. These acids may also contain one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. Mention may in particular be made of acetic acid or propionic acid, terephthalic acid, as well as citric acid and tartaric acid.
Selon un mode de réalisation de l'invention, le polymère éthylenique greffé ne contient pas de monomères vinyliques non acryliques additionnels tels que décrits précédemment. Dans ce mode de réalisation, le squelette insoluble du polymère éthylenique greffé est formé uniquement de monomères acryliques tels que décrits précédemment. Il est entendu que ces monomères acryliques non polymérisés peuvent être solubles dans le milieu de dispersion considéré, mais le polymère formé avec ces monomères est insoluble dans le milieu de dispersion.According to one embodiment of the invention, the grafted ethylenic polymer does not contain additional non-acrylic vinyl monomers as described above. In this embodiment, the insoluble skeleton of the grafted ethylenic polymer is formed only from acrylic monomers as described above. It is understood that these non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with these monomers is insoluble in the dispersion medium.
Comme monomère acrylique principal, on peut utiliser l'acrylate de méthyle, le méthacrylate de méthyle, l'acrylate d'éthyle, le méthacrylate d'éthyle, l'acrylate de n- propyle, le méthacrylate de n-propyle, l'acrylate d'iso-propyle et le méthacrylate d'iso- propyle, et leurs mélanges.As the main acrylic monomer, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, acrylate can be used. isopropyl and isopropyl methacrylate, and mixtures thereof.
On préfère tout particulièrement l'acrylate de méthyle, le méthacrylate de méthyle, le méthacrylate d'éthyle.Particular preference is given to methyl acrylate, methyl methacrylate and ethyl methacrylate.
Les monomères acryliques additionnels peuvent être choisis parmi :The additional acrylic monomers can be chosen from:
- l'acide (méth)acrylique et ses sels,- (meth) acrylic acid and its salts,
- les (méth)acrylates de formule (I) et leurs sels :- the (meth) acrylates of formula (I) and their salts:
H2C=C COOR'2 H 2 C = C COOR ' 2
(I)(I)
R '',1R '', 1
dans laquelle :in which :
- R'ι désigne un atome d'hydrogène ou un groupe méthyle ; - R'2 représente- R'ι denotes a hydrogen atom or a methyl group; - R ' 2 represents
- un groupe alkyle linéaire ou ramifié comprenant de 1 à 6 atomes de carbone, ledit groupe comportant dans sa chaîne un ou plusieurs atomes d'oxygène et/ou comportant un ou plusieurs substituants choisis parmia linear or branched alkyl group comprising from 1 to 6 carbon atoms, said group comprising in its chain one or more oxygen atoms and / or comprising one or more substituents chosen from
-OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C-J-C3 ;-OH, halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched C-J-C3 alkyl;
- un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs atomes d'oxygène et/ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I) ;- a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more oxygen atoms and / or possibly comprising one or more substituents chosen from OH and the halogen atoms (F, Cl, Br, I);
- et leurs mélanges.- and their mixtures.
A titre d'exemples de R'2, on peut citer le groupe methoxyéthyle, ethoxyéthyle, trifluoroéthyle; 2-hydroxyéthyle, 2-hydroxypropyle, diméthylaminoéthyle, diéthylaminoéthyle, diméthylaminopropyle.As examples of R ′ 2 , mention may be made of the methoxyethyl, ethoxyethyl, trifluoroethyl group; 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl.
Parmi ces monomères acryliques additionnels, on peut tout particulièrement citer l'acide (méth)acrylique, les (méth)acrylates de methoxyéthyle ou d'éthoxyéthyle; le méthacrylate de trifluoroéthyle; le méthacrylate de diméthylaminoéthyle, le méthacrylate de diéthylaminoéthyle, le méthacrylate de 2-hydroxypropyle, le méthacrylate de 2- hydroxyéthyle, l'acrylate de 2-hydroxypropyle, l'acrylate de 2-hydroxyéthyle, leurs sels, et leurs mélanges. On préfère tout particulièrement l'acide acrylique, l'acide méthylacrylique.Among these additional acrylic monomers, mention may very particularly be made of (meth) acrylic acid, methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, their salts, and mixtures thereof. Particularly preferred is acrylic acid, methylacrylic acid.
Les macromonomères comportent à une des extrémités de la chaîne un groupe terminal polymérisable apte à réagir au cours de la polymérisation avec les monomères acryliques et éventuellement les monomères vinyliques additionnels, pour former les chaînes latérales du polymère éthylenique greffé. Ledit groupe terminal polymérisable peut être en particulier un groupe vinyle ou (méth)acrylate (ou (méth)acryloxy), et de préférence un groupe (méth)acrylate.The macromonomers comprise at one end of the chain a polymerizable end group capable of reacting during the polymerization with the acrylic monomers and optionally the additional vinyl monomers, to form the side chains of the grafted ethylenic polymer. Said polymerizable end group may in particular be a vinyl or (meth) acrylate (or (meth) acryloxy) group, and preferably a (meth) acrylate group.
Les macromonomères sont choisis préférentiellement parmi les macromonomères dont l'homopolymère a une température de transition vitreuse (Tg) inférieure ou égale à 25°C, notamment allant de - 100°C à 25°C, de préférence allant de - 80°C à 0°C. Les macromonomères ont une masse moléculaire moyenne en poids supérieure ou égale à 200, de préférence supérieure ou égale à 300, préférentiellement supérieure ou égale à 500, et plus préférentiellement supérieure à 600.The macromonomers are preferably chosen from macromonomers whose homopolymer has a glass transition temperature (Tg) less than or equal to 25 ° C, in particular ranging from - 100 ° C to 25 ° C, preferably ranging from - 80 ° C to 0 ° C. The macromonomers have a weight average molecular mass greater than or equal to 200, preferably greater than or equal to 300, preferably greater than or equal to 500, and more preferably greater than 600.
De préférence, les macromonomères ont une masse moléculaire moyenne en poids (Mw) allant de 200 à 100 000, de préférence allant de 500 à 50 000, préférentiellement allant de 800 à 20 000, plus préférentiellement allant de 800 à 10000, et encore plus préférentiellement allant de 800 à 6000.Preferably, the macromonomers have a weight average molecular weight (Mw) ranging from 200 to 100,000, preferably ranging from 500 to 50,000, preferably ranging from 800 to 20,000, more preferably ranging from 800 to 10,000, and even more preferably ranging from 800 to 6000.
Dans la présente demande, les masses molaires moyennes en poids (Mw) et en nombre (Mn) sont déterminées par chromatographie liquide par perméation de gel (solvant THF, courbe d'étalonnage établie avec des étalons de polystyrène linéaire, détecteur réfractométrique).In the present application, the average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
Comme macromonomères carbonés, on peut en particulier citer :As carbon macromonomers, mention may in particular be made of:
-(i) les homopolymères et les copolymères (méth)acrylate d'alkyle linéaire ou ramifié en C8-C22, présentant un groupe terminal polymérisable choisi parmi les groupes vinyle ou (méth)acrylate parmi lesquels on peut citer en particulier : les macromonomères de poly(acrylate d'éthyl-2 hexyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(acrylate de dodécyle) ou de poly(méthacrylate de dodécyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(acrylate de stéaryle) ou de poly (méthacrylate de stéaryle) à extrémité mono(méth)acrylate.(i) linear or branched C8-C22 homopolymers and copolymers (meth) acrylate of alkyl, having a polymerizable end group chosen from vinyl or (meth) acrylate groups among which there may be mentioned in particular: the macromonomers of poly (2-ethylhexyl acrylate) with mono (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers with mono (meth) acrylate end; poly (stearyl acrylate) or poly (stearyl methacrylate) macromonomers with mono (meth) acrylate end.
De tels macromonomères sont notamment décrits dans les brevets EP895467 et EP96459 et dans l'article Gillman K.F., Polymer Letters, Vol 5, page 477-481 (1967).Such macromonomers are in particular described in patents EP895467 and EP96459 and in the article Gillman K.F., Polymer Letters, Vol 5, page 477-481 (1967).
On peut en particulier citer les macromonomères à base de poly(acrylate d'éthyl-2-hexyle) ou de poly(acrylate de dodécyle) à extrémité mono(méth)acrylate. -(ii) les polyoléfines ayant un groupe terminal à insaturation éthylenique , en particulier ayant un groupement terminal (méth)acrylate. Comme exemple de telles polyoléfines, on peut citer en particulier les macromonomères suivants, étant entendu qu'ils ont un groupe terminal (méth)acrylate : les macromonomères de polyethylene, les macromonomères de polypropylène, les macromonomères de copolymère polyéthylène/polypropylène, les macromonomères de copolymère polyéthylène/polybutylène, les macromonomères de polyisobutylène ; les macromonomères de polybutadiène; les macromonomères de polyisoprène ; les macromonomères de polybutadiène; les macromonomères de poly(éthylène/butylène)-polyisoprène ;Mention may in particular be made of macromonomers based on poly (ethyl-2-hexyl acrylate) or poly (dodecyl acrylate) with a mono (meth) acrylate end. - (ii) polyolefins having a terminal group containing ethylenic unsaturation, in particular having a terminal group (meth) acrylate. As an example of such polyolefins, mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: macromonomers of polyethylene, macromonomers of polypropylene, macromonomers of polyethylene / polypropylene copolymer, macromonomers of polyethylene / polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers;
De tels macromonomères sont en particulier décrits dans US5625005 qui mentionne des macromonomères éthylène/butylene et éthylène/propylène à groupement terminal réactif (méth)acrylate.Such macromonomers are in particular described in US5625005 which mentions ethylene / butylene and ethylene / propylene macromonomers with reactive (meth) acrylate end group.
On peut en particulier citer le méthacrylate de poly(éthylène/butylène), tel que celui commercialisé sous la dénomination Kraton Liquid L-1253 par Kraton Polymers.Mention may in particular be made of poly (ethylene / butylene) methacrylate, such as that marketed under the name Kraton Liquid L-1253 by Kraton Polymers.
De préférence, le macromonomère polymérisé (constituant les chaînes latérales du polymère greffé) représente de 0,1 à 15 % en poids du poids total du polymère, préférentiellement de 0,2 à 10 % en poids, et plus préférentiellement de 0,3 à 8 % en poids.Preferably, the polymerized macromonomer (constituting the side chains of the grafted polymer) represents from 0.1 to 15% by weight of the total weight of the polymer, preferably from 0.2 to 10% by weight, and more preferably from 0.3 to 8% by weight.
Comme polymère éthylenique greffé particulièrement préféré dispersé dans une phase grasse liquide non siliconée, on peut utiliser ceux obtenus par polymérisation : - de l'acrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans un solvant choisi parmi l'isododécane, l'isononanoate d'isononyle, l'octyldodécanol , le malate de diisostéaryle, un benzoate d'alkyl C12-C15 (tel que Finsolv TN) ;As a particularly preferred grafted ethylenic polymer dispersed in a non-silicone liquid fatty phase, those obtained by polymerization can be used: - methyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in a solvent chosen from isododecane, isononyl isononanoate, octyldodecanol, diisostearyl, a C 12 -C 15 alkyl benzoate (such as Finsolv TN);
- de l'acrylate de methoxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ;- methoxyethyl acrylate and a polyethylene / polybutylene macromonomer with a methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L- 1253), en particulier dans l'isododécane ;- Methyl acrylate / methyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / acide acrylique et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L- 1253), en particulier dans l'isododécane ;- Methyl acrylate / acrylic acid monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de diméthylaminoéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane ;- Methyl acrylate / dimethylaminoethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de 2-hydroxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate (notamment Kraton L-1253), en particulier dans l'isododécane.- Methyl acrylate / 2-hydroxyethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group (in particular Kraton L-1253), in particular in isododecane.
De préférence, le polymère greffé a une masse moléculaire moyenne en poids (Mw) comprise entre 10 000 et 300 000, notamment entre 20 000 et 200 000, mieux encore entre 25 000 et 150 000.Preferably, the grafted polymer has a weight-average molecular mass (Mw) of between 10,000 and 300,000, especially between 20,000 and 200,000, better still between 25,000 and 150,000.
Grâce aux caractéristiques susmentionnées, dans un milieu organique de dispersion donné, les polymères ont la capacité de se replier sur eux-mêmes, formant ainsi des particules de forme sensiblement sphérique, avec sur le pourtour de ces particules les chaînes latérales déployées, qui assurent la stabilité de ces particules. De telles particules résultant des caractéristiques du polymère greffé ont la particularité de ne pas s'agglomérer dans ledit milieu et donc de s'autostabiliser et de former une dispersion de particules de polymère particulièrement stable.Thanks to the abovementioned characteristics, in a given organic dispersion medium, the polymers have the capacity to fold in on themselves, thus forming particles of substantially spherical shape, with around the periphery of these particles the deployed side chains, which ensure the stability of these particles. Such particles resulting from the characteristics of the grafted polymer have the particularity of not agglomerating in said medium and therefore of self-stabilizing and of forming a dispersion of particularly stable polymer particles.
En particulier, les polymères éthyléniques greffés de la dispersion peuvent former des particules nanométriques, de taille moyenne allant de 10 à 400 nm, de préférence de 20 à 200 nm.In particular, the grafted ethylenic polymers of the dispersion can form nanometric particles, of average size ranging from 10 to 400 nm, preferably from 20 to 200 nm.
Du fait de cette taille très faible, les particules de polymère greffé en dispersion sont particulièrement stables et donc peu susceptibles de former des agglomérats.Because of this very small size, the particles of polymer grafted in dispersion are particularly stable and therefore unlikely to form agglomerates.
La dispersion de polymère greffé peut donc être une dispersion stable et ne forme pas de sédiments, lorsqu'elle est placée pendant une durée prolongée (par exemple 24 heures) à température ambiante (25 °C).The dispersion of grafted polymer can therefore be a stable dispersion and does not form sediments, when it is placed for a prolonged period (for example 24 hours) at room temperature (25 ° C).
De préférence, la dispersion de particules de polymère greffé présente un taux de matière sèche (ou extrait sec) en polymère pouvant aller de 40 % à 70 % en poids de matière sèche, notamment allant de 45 % à 65 % en poids.Preferably, the dispersion of particles of grafted polymer has a content of dry matter (or dry extract) in polymer which can range from 40% to 70% by weight of dry matter, in particular ranging from 45% to 65% by weight.
On peut préparer la dispersion de particules de polymère greffé par un procédé comprenant une étape de copolymérisation radicalaire, dans un milieu organique de polymérisation, d'un ou plusieurs monomères acryliques tels que définis précédemment avec un ou plusieurs macromonomères tels que définis précédemment. Comme indiqué précédemment, le milieu organique liquide de dispersion peut être identique ou différent du milieu de polymérisation.The dispersion of grafted polymer particles can be prepared by a process comprising a step of radical copolymerization, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above. As indicated above, the liquid organic dispersion medium can be identical to or different from the polymerization medium.
D'une manière classique, la copolymérisation peut être effectuée en présence d'un initiateur de polymérisation. Les initiateurs de polymérisation peuvent être des amorceurs radicalaires. De manière générale, un tel initiateur de polymérisation peut être choisi parmi les composés organiques peroxydes tels que le dilauroyl peroxyde, le dibenzoyl peroxyde, le tert-butyl peroxy-2-éthylhexanoate ; les composés diazotés tels que l'azobisisobutyronitrile, l'azobisdiméthylvalero-nitrile. La réaction peut être également initiée à l'aide de photoinitiateurs ou par une radiation telle que des UV, des neutrons ou par plasma.Conventionally, the copolymerization can be carried out in the presence of a polymerization initiator. The polymerization initiators can be radical initiators. In general, such a polymerization initiator can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate; diazotized compounds such as azobisisobutyronitrile, azobisdimethylvalero-nitrile. The reaction can also be initiated using photoinitiators or by radiation such as UV, neutrons or plasma.
D'une manière générale, pour mettre en œuvre ce procédé, on introduit, dans un réacteur de taille appropriée à la quantité de polymère que l'on va réaliser, au moins une partie du milieu organique de polymérisation, une partie des monomères acryliques et/ou vinyliques additionnels, qui constituera, après polymérisation, le squelette insoluble, la totalité du macromonomère (qui constituera les chaînes latérales du polymère) et une partie de l'initiateur de polymérisation. A ce stade d'introduction, le milieu reactionnel forme un milieu relativement homogène. Le milieu reactionnel est ensuite agité et chauffé jusqu'à une température pour obtenir une polymérisation des monomères et macromonomères. Après un certain temps, le milieu initialement homogène et limpide conduit à une dispersion d'aspect laiteux. On ajoute ensuite un mélange constitué de la partie restante de monomères et de l'initiateur de polymérisation. Après un temps adéquat pendant lequel le mélange est chauffé sous agitation, le milieu se stabilise sous forme d'une dispersion laiteuse, la dispersion comprenant des particules de polymères stabilisés dans le milieu dans lequel elles ont été créées, ladite stabilisation étant due à la présence, dans le polymère, de chaînes latérales solubles dans ledit milieu de dispersion.In general, to carry out this process, at least part of the organic polymerization medium is introduced into a reactor of a size appropriate to the quantity of polymer that is to be produced, and / or additional vinyls, which will constitute, after polymerization, the insoluble skeleton, all of the macromonomer (which will constitute the side chains of the polymer) and part of the polymerization initiator. At this stage of introduction, the reaction medium forms a relatively homogeneous medium. The reaction medium is then stirred and heated to a temperature to obtain a polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion with a milky appearance. A mixture consisting of the remaining part of the monomers and of the polymerization initiator is then added. After an adequate time during which the mixture is heated with stirring, the medium stabilizes in the form of a milky dispersion, the dispersion comprising particles of polymers stabilized in the medium in which they were created, said stabilization being due to the presence , in the polymer, of side chains soluble in said dispersion medium.
Le polymère greffé peut être présent dans la composition selon l'invention en une teneur en matière sèche (ou matière active) allant de 1 à 70% en poids par rapport au poids total de la composition, mieux de 5 à 60% en poids, de préférence allant de 6 à 45% et mieux allant de 8 à 40% en poids.The grafted polymer may be present in the composition according to the invention in a dry matter (or active material) content ranging from 1 to 70% by weight relative to the total weight of the composition, better still from 5 to 60% by weight, preferably ranging from 6 to 45% and better still ranging from 8 to 40% by weight.
La composition selon l'invention peut également comprendre au moins corps gras solides à température ambiante notamment choisi parmi les cires, les corps gras pâteux, les gommes et leurs mélanges. Ces corps gras peuvent être d'origine animale, végétale, minérale ou synthétique.The composition according to the invention may also comprise at least fatty substances which are solid at room temperature, in particular chosen from waxes, pasty fatty substances, gums and their mixtures. These fatty substances can be of animal, vegetable, mineral or synthetic origin.
CireWax
La composition selδon l'invention peut comprendre une cire ou un mélange de cires. La cire considérée dans le cadre de la présente invention est d'une manière générale un composé lipophile, solide à température ambiante (25 °C), à changement d'état solide/liquide réversible, ayant un point de fusion supérieur ou égal à 30 °C pouvant aller jusqu'à 120 °C.The composition according to the invention may comprise a wax or a mixture of waxes. The wax considered in the context of the present invention is generally a lipophilic compound, solid at room temperature (25 ° C), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C up to 120 ° C.
En portant la cire à l'état liquide (fusion), il est possible de la rendre miscible aux huiles et de former un mélange homogène microscopiquement, mais en ramenant la température du mélange à la température ambiante, on obtient une recristallisation de la cire dans les huiles du mélange.By bringing the wax to the liquid state (fusion), it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized in the oils in the mixture.
En particulier, les cires convenant à l'invention peuvent présenter un point de fusion supérieur à 45° environ, et en particulier supérieur à 55 °C.In particular, the waxes suitable for the invention can have a melting point greater than approximately 45 °, and in particular greater than 55 ° C.
Le point de fusion de la cire peut être mesuré à l'aide d'un calorimètre à balayage différentiel (D.S.C.), par exemple le calorimètre vendu sous la dénomination DSC 30 par la société METLER. Le protocole de mesure est le suivant :The melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METLER. The measurement protocol is as follows:
Un échantillon de 15 mg de produit disposé dans un creuset est soumis à une première montée en température allant de 0 °C à 120 °C, à la vitesse de chauffe de 10 °C/ minute, puis est refroidi de 120 °C à 0 °C à une vitesse de refroidissement de 10 °C/minute et enfin soumis à une deuxième montée en température allant de 0 °C à 120 °C à une vitesse de chauffe de 5 °C/minute. Pendant la deuxième montée en température, on mesure la variation de la différence de puissance absorbée par le creuset vide et par le creuset contenant l'échantillon de produit en fonction de la température. Le point de fusion du composé est la valeur de la température correspondant au sommet du pic de la courbe représentant la variation de la différence de puissance absorbée en fonction de la température.A 15 mg sample of product placed in a crucible is subjected to a first temperature rise ranging from 0 ° C to 120 ° C, at the heating rate of 10 ° C / minute, then is cooled from 120 ° C to 0 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise ranging from 0 ° C to 120 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the product sample is measured as a function of the temperature. Point of melting of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of the temperature.
Les cires susceptibles d'être utilisées dans les compositions selon l'invention sont choisies parmi les cires, solides et rigides à température ambiante, d'origine animale, végétale, minérale ou de synthèse et leurs mélanges.The waxes capable of being used in the compositions according to the invention are chosen from waxes, solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin and their mixtures.
La cire peut également présenter une dureté allant de 0,05 MPa à 30 MPa, et de préférence allant de 6 MPa à 15 MPa . La dureté est déterminée par la mesure de la force en compression mesurée à 20 °C à l'aide du texturometre vendu sous la dénomination TA-TX2i par la société RHEO, équipé d'un cylindre en inox d'un diamètre de 2 mm se déplaçant à la vitesse de mesure de 0,1 mm/s, et pénétrant dans la cire à une profondeur de pénétration de 0,3 mm. Le protocole de mesure est le suivant :The wax can also have a hardness ranging from 0.05 MPa to 30 MPa, and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force measured at 20 ° C using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm. moving at the measuring speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm. The measurement protocol is as follows:
La cire est fondue à une température égale au point de fusion de la cire + 20 °C. La cire fondue est coulée dans un récipient de 30 mm de diamètre et de 20 mm de profondeur. La cire est recristallisée à température ambiante (25 °C) pendant 24 heures, puis la cire est conservée pendant au moins 1 heure à 20 °C avant d'effectuer la mesure de dureté. La valeur de la dureté est la force de compression maximale mesurée divisée par la surface du cylindre du texturometre en contact avec la cire.The wax is melted at a temperature equal to the melting point of the wax + 20 ° C. The melted wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C) for 24 hours, then the wax is stored for at least 1 hour at 20 ° C before carrying out the hardness measurement. The hardness value is the maximum compression force measured divided by the surface area of the texturometer cylinder in contact with the wax.
On peut notamment utiliser les cires hydrocarbonées comme la cire d'abeilles, la cire de lanoline, et les cires d'insectes de Chine; la cire de riz, la cire de Carnauba, la cire de Candellila, la cire d'Ouricurry, la cire d'Alfa, la cire de fibres de liège, la cire de canne à sucre, la cire du Japon et la cire de sumac; la cire de montan, les cires microcristallines, les paraffines et l'ozokérite; les cires de polyethylene, les cires obtenues par la synthèse de Fisher-Tropsch et les copolymères cireux ainsi que leurs esters. On peut aussi citer les cires obtenues par hydrogénation catalytique d'huiles animales ou végétales ayant des chaînes grasses, linéaires ou ramifiées, en C8-C32.It is possible in particular to use hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candellila wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax ; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by the Fisher-Tropsch synthesis and waxy copolymers and their esters. Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, of C8-C32.
Parmi celles-ci, on peut notamment citer l'huile de jojoba hydrogénée, l'huile de jojoba isomérisée telle que l'huile de jojoba partiellement hydrogénée isomérisée trans fabriquée ou commercialisée par la société Désert Whale sous la référence commerciale ISO-Among these, mention may in particular be made of hydrogenated jojoba oil, isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by the company Désert Whale under the commercial reference ISO-
JOJOBA-50®, l'huile de tournesol hydrogénée, l'huile de ricin hydrogénée, l'huile de coprah hydrogénée et l'huile de lanoline hydrogénée, le tétrastéarate de di-(triméthylol-JOJOBA-50 ® , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di- (trimethylol-) tetrastearate
1 ,1,1 propane) vendu sous la dénomination « HEST 2T-4S » par la société HETERENE, le tétrabéhénate de di-(triméthylol- 1 ,1 ,1 propane) vendue sous la dénomination HEST 2T- 4B par la société HETERENE.1, 1.1 propane) sold under the name "HEST 2T-4S" by the company HETERENE, di- (trimethylol-1, 1, 1 propane) tetrabehenate sold under the name HEST 2T- 4B by the company HETERENE.
On peut encore citer les cires de silicone comme les alkyl ou alkoxy-diméticone ayant deMention may also be made of silicone waxes such as alkyl or alkoxy-dimethicone having
16 à 45 atomes de carbone, les cires fluorées.16 to 45 carbon atoms, fluorinated waxes.
On peut également utiliser la cire obtenue par hydrogénation d'huile d'olive estérifiée avec l'alcool stéarylique vendue sous la dénomination « PHYTOWAX OliveIt is also possible to use the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name "PHYTOWAX Olive
18 L 57 » ou bien encore les cires obtenues par hydrogénation d'huile de ricin estérifiée avec l'alcool cetylique vendus sous la dénomination « PHYTOWAX ricin 16L64 et18 L 57 "or else the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the name" PHYTOWAX ricin 16L64 and
22L73 », par la société SOPHIM. De telles cires sont décrites dans la demande FR-A-22L73 ”, by the company SOPHIM. Such waxes are described in application FR-A-
2792190.2792190.
Selon un mode de réalisation particulier, les compositions selon l'invention peuvent comprendre au moins une cire dite cire collante c'est-à-dire possédant un collant supérieur ou égal à 0,7 N.s et une dureté inférieure ou égale à 3,5 MPa. L'utilisation d'une cire collante peut notamment permettre l'obtention d'une composition cosmétique qui s'applique facilement sur les fibres kératiniques, ayant une bonne accroche sur les fibres kératiniques et qui conduit à la formation d'un maquillage lisse, homogène et épaississant. La cire collante utilisée peut posséder notamment un collant allant de 0,7 N.s à 30 N.s, en particulier supérieur ou égal à 1 N.s, notamment allant de 1 N.s à 20 N.s, en particulier supérieur ou égal à 2 N.s, notamment allant de 2 N.s à 10 N.s, et en particulier allant de 2According to a particular embodiment, the compositions according to the invention can comprise at least one so-called sticky wax, that is to say having a stickiness greater than or equal to 0.7 Ns and a hardness less than or equal to 3.5 MPa. The use of a sticky wax can in particular make it possible to obtain a cosmetic composition which is easily applied to keratin fibers, having good adhesion to keratin fibers and which leads to the formation of a smooth, homogeneous makeup. and thickener. The sticky wax used may in particular have a tack ranging from 0.7 Ns to 30 Ns, in particular greater than or equal to 1 Ns, in particular ranging from 1 Ns to 20 Ns, in particular greater than or equal to 2 Ns, in particular ranging from 2 Ns to 10 Ns, and in particular ranging from 2
N.s à 5 N.s.N.s to 5 N.s.
Le collant de la cire est déterminé par la mesure de l'évolution de la force (force de compression ou force d'etirement) en fonction du temps, à 20 °C à l'aide du texturometre vendu sous la dénomination « TA-TX2i® » par la société RHEO, équipé d'un mobile en polymère acrylique en forme de cône formant un angle de 45°.The stickiness of the wax is determined by measuring the evolution of the force (compression force or stretching force) as a function of time, at 20 ° C. using the texturometer sold under the name "TA-TX2i ® ”by the company RHEO, equipped with a mobile in acrylic polymer in the shape of a cone forming an angle of 45 °.
Le protocole de mesure est le suivant : La cire est fondue à une température égale au point de fusion de la cire + 10 °C. La cire fondue est coulée dans un récipient de 25 mm de diamètre et de 20 mm de profondeur. La cire est recristallisée à température ambiante (25 °C) pendant 24 heures de telle sorte que la surface de la cire soit plane et lisse, puis la cire est conservée pendant au moins 1 heure à 20 °C avant d'effectuer la mesure du collant. Le mobile du texturometre est déplacé à la vitesse de 0,5 mm/s, puis pénètre dans la cire jusqu'à une profondeur de pénétration de 2 mm. Lorsque le mobile a pénétré dans la cire à la profondeur de 2 mm, le mobile est maintenu fixe pendant 1 seconde (correspondant au temps de relaxation) puis est retiré à la vitesse de 0,5 mm/s. Pendant le temps de relaxation, la force (force de compression) décroît fortement jusqu'à devenir nulle puis, lors du retrait du mobile, la force (force d'etirement) devient négative pour ensuite croître à nouveau vers la valeur 0. Le collant correspond à l'intégrale de la courbe de la force en fonction du temps pour la partie de la courbe correspondant aux valeurs négatives de la force (force d'etirement). La valeur du collant est exprimée en N.s.The measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 10 ° C. The melted wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C) for 24 hours so that the surface of the wax is flat and smooth, then the wax is stored for at least 1 hour at 20 ° C before measuring the tights. The mobile of the texturometer is moved at the speed of 0.5 mm / s, then enters the wax to a penetration depth of 2 mm. When the mobile has penetrated into the wax to the depth of 2 mm, the mobile is held fixed for 1 second (corresponding to the relaxation time) then is removed at the speed of 0.5 mm / s. During the relaxation time, the force (compression force) decreases sharply until it becomes zero, then, when the mobile is removed, the force (stretching force) becomes negative and then increases again towards the value 0. The tights corresponds to the integral of the force curve as a function of time for the part of the curve corresponding to the negative values of the force (stretching force). The value of the tights is expressed in N.s.
La cire collante pouvant être utilisée a généralement une dureté inférieure ou égale à 3,5 MPa, en particulier allant de 0,01 MPa à 3,5 MPa, notamment allant de 0,05 MPa à 3 MPa, voire encore allant de 0,1 MPa à 2,5 MPa. La dureté est mesurée selon le protocole décrit précédemment.The sticky wax that can be used generally has a hardness less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, in particular ranging from 0.05 MPa to 3 MPa, or even ranging from 0, 1 MPa to 2.5 MPa. The hardness is measured according to the protocol described above.
Comme cire collante, on peut utiliser un (hydroxystéaryloxy)stéarate d'alkyle en C20-C40 As a sticky wax, it is possible to use a C 20 -C 40 alkyl (hydroxystearyloxy) stearate.
(le groupe alkyle comprenant de 20 à 40 atomes de carbone), seul ou en mélange, en particulier un 12-(12'-hydroxystéaryloxy)stéarate d'alkyle en C20-C40, de formule (II) :(the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, in particular a 12- (12′-hydroxystearyloxy) C 20 -C 40 alkyl stearate, of formula (II):
Figure imgf000035_0001
Figure imgf000035_0001
dans laquelle m est un entier allant de 18 à 38, ou un mélange de composés de formule (II).in which m is an integer ranging from 18 to 38, or a mixture of compounds of formula (II).
Une telle cire est notamment vendue sous les dénominations « Kester Wax K 82 P® » et « Kester Wax K 80 P® » par la société KOSTER KEUNEN. Les cires citées ci-dessus présentent généralement un point de fusion commençante inférieur à 45 °C.Such a wax is sold in particular under the names "Kester Wax K 82 P ® " and "Kester Wax K 80 P ® " by the company KOSTER KEUNEN. The waxes mentioned above generally have a starting melting point below 45 ° C.
La ou les cires peu(ven)t être présente(s) sous forme d'une microdispersion aqueuse de cire. On entend par microdispersion aqueuse de cire, une dispersion aqueuse de particules de cire, dans laquelle la taille desdites particules de cire est inférieure ou égale à environ 1 μm.The wax (es) can be present in the form of an aqueous microdispersion of wax. The expression aqueous wax microdispersion is understood to mean an aqueous dispersion of wax particles, in which the size of said wax particles is less than or equal to approximately 1 μm.
Les microdispersions de cire sont des dispersions stables de particules colloïdales de cire, et sont notamment décrites dans "Microemulsions Theory and Practice", L.M. Prince Ed., Académie Press (1977) pages 21-32.Wax microdispersions are stable dispersions of colloidal wax particles, and are described in particular in "Microemulsions Theory and Practice", L.M. Prince Ed., Académie Press (1977) pages 21-32.
En particulier, ces microdispersions de cire peuvent être obtenues par fusion de la cire en présence d'un tensioactif, et éventuellement d'une partie de l'eau, puis addition progressive d'eau chaude avec agitation. On observe la formation intermédiaire d'une émulsion du type eau-dans-huile, suivie d'une inversion de phase avec obtention finale d'une microémulsion du type huile-dans-eau. Au refroidissement, on obtient une microdispersion stable de particules colloïdales solides de cire.In particular, these wax microdispersions can be obtained by melting the wax in the presence of a surfactant, and optionally part of the water, then progressive addition of hot water with stirring. The intermediate formation of a water-in-oil type emulsion is observed, followed by a phase inversion with final production. of an oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal wax particles is obtained.
Les microdispersion de cire peuvent également être obtenues par agitation du mélange de cire, de tensioactif et d'eau à l'aide de moyen d'agitation tels que les ultrasons, l'homogénéisateur haute pression, les turbines.The wax microdispersion can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high pressure homogenizer, turbines.
Les particules de la microdispersion de cire ont de préférence des dimensions moyennes inférieures à 1 μm (notamment allant de 0,02 μm à 0,99 μm), de préférence inférieures à 0,5 μm (notamment allant de 0,06 μm à 0,5 μm). Ces particules sont constituées essentiellement d'une cire ou d'un mélange de cires. Elles peuvent toutefois comprendre en proportion minoritaire des additifs gras huileux et/ou pâteux, un tensioactif et/ou un additif/actif liposoluble usuel.The particles of the wax microdispersion preferably have mean dimensions of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably less than 0.5 μm (in particular ranging from 0.06 μm to 0 , 5 μm). These particles consist essentially of a wax or a mixture of waxes. They may, however, in a minor proportion comprise oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active.
Par corps gras pâteux, on entend un composé gras lipophile comportant à la température de 23°C une fraction liquide et une fraction solide.The term “pasty fatty substance” means a lipophilic fatty compound comprising at the temperature of 23 ° C. a liquid fraction and a solid fraction.
Ledit composé pâteux a de préférence une dureté à 20°C allant de 0,001 à 0,5 MPa, de préférence de 0,002 à 0,4 MPa.Said pasty compound preferably has a hardness at 20 ° C ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.
La dureté est mesurée selon une méthode de pénétration d'une sonde dans un échantillon de composé et en particulier à l'aide d'un analyseur de texture (par exemple le TA-XT2i de chez Rhéo) équipé d'un cylindre en inox de 2 mm de diamètre. La mesure de dureté est effectuée à 20°C au centre de 5 échantillons. Le cylindre est introduit dans chaque échantillon à une pré-vitesse de 1 mm/s puis à une vitesse de mesure de 0,1 mm/s, la profondeur de pénétration étant de 0,3 mm. La valeur relevée de la dureté est celle du pic maximum.The hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyzer (for example TA-XT2i from Rhéo) equipped with a stainless steel cylinder of 2 mm in diameter. The hardness measurement is carried out at 20 ° C in the center of 5 samples. The cylinder is introduced into each sample at a pre-speed of 1 mm / s and then at a measurement speed of 0.1 mm / s, the penetration depth being 0.3 mm. The value recorded for the hardness is that of the maximum peak.
La fraction liquide du composé pâteux .mesurée à 23°C représente de préférence 9 à 97% en poids du composé. Cette fraction liquide à 23°C représente de préférence entre 15 et 85%, de préférence encore entre 40 et 85% en poids. La fraction liquide en poids du composé pâteux à 23°C est égale au rapport de l'enthalpie de fusion consommée àThe liquid fraction of the pasty compound. Measured at 23 ° C. preferably represents 9 to 97% by weight of the compound. This liquid fraction at 23 ° C preferably represents between 15 and 85%, more preferably between 40 and 85% by weight. The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed to
23°C sur l'enthalpie de fusion du composé pâteux.23 ° C on the enthalpy of fusion of the pasty compound.
L'enthalpie de fusion du composé pâteux est l'enthalpie consommée par le composé pour passer de l'état solide à l'état liquide. Le composé pâteux est dit à l'état solide lorsque l'intégralité de sa masse est sous forme solide cristalline. Le composé pâteux est dit à l'état liquide lorsque l'intégralité de sa masse est sous forme liquide.The enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in crystalline solid form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form.
L'enthalpie de fusion du composé pâteux est égale à l'aire sous la courbe du thermogramme obtenu à l'aide d'un calorimètre à balayage différentiel (D. S. C), tel que le calorimètre vendu sous la dénomination MDSC 2920 par la société TA instrument, avec une montée en température de 5 ou 10°C par minute, selon la norme ISO 11357- 3:1999. L'enthalpie de fusion du composé pâteux est la quantité d'énergie nécessaire pour faire passer le composé de l'état solide à l'état liquide. Elle est exprimée eu J/g. L'enthalpie de fusion consommée à 23°C est la quantité d'énergie absorbée par l'échantillon pour passer de l'état solide à l'état qu'il présente à 23°C constitué d'une fraction liquide et d'une fraction solide.The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10 ° C per minute, according to ISO 11357-3: 1999. The enthalpy of fusion of the pasty compound is the amount of energy required to bring the compound from the solid state to the liquid state. It is expressed in J / g. The enthalpy of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to go from the solid state to the state it presents at 23 ° C consisting of a liquid fraction and a solid fraction.
La fraction liquide du composé pâteux mesurée à 32°C représente de préférence de 30 à 100% en poids du composé, de préférence de 80 à 100%, de préférence encore de 90 à 100% en poids du composé. Lorsque la fraction liquide du composé pâteux mesurée à 32°C est égale à 100%, la température de la fin de la plage de fusion du composé pâteux est inférieure ou égale à 32°C.The liquid fraction of the pasty compound measured at 32 ° C. preferably represents from 30 to 100% by weight of the compound, preferably from 80 to 100%, more preferably from 90 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32 ° C is equal to 100%, the temperature at the end of the melting range of the pasty compound is less than or equal to 32 ° C.
La fraction liquide du composé pâteux mesurée à 32°C est égale au rapport de l'enthalpie de fusion consommée à 32°C sur l'enthalpie de fusion du composé pâteux. L'enthalpie de fusion consommée à 32°C est calculée de la même façon que l'enthalpie de fusion consommée à 23°C.The liquid fraction of the pasty compound measured at 32 ° C is equal to the ratio of the enthalpy of fusion consumed at 32 ° C to the enthalpy of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C is calculated in the same way as the enthalpy of fusion consumed at 23 ° C.
Les gommes sont généralement des polydiméthylsiloxanes (PDMS) à haut poids moléculaire ou des gommes de cellulose ou des polysaccharides et les corps pâteux sont généralement des composés hydrocarbonés comme les lanolines et leurs dérivés ou encore des PDMS.The gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and pasty bodies are generally hydrocarbon compounds such as lanolines and their derivatives or even PDMSs.
La nature et la quantité des corps solides sont fonction des propriétés mécaniques et des textures recherchées. A titre indicatif, la composition peut contenir de 0,1 à 50 % en poids de cires, par rapport au poids total de la composition, mieux de 1 à 40 % et encore mieux de 5 à 30% en poids.The nature and quantity of the solid bodies are a function of the mechanical properties and of the desired textures. As an indication, the composition may contain from 0.1 to 50% by weight of waxes, relative to the total weight of the composition, better from 1 to 40% and even better still from 5 to 30% by weight.
La composition peut comprendre, outre le polymère en dispersion dans la phase grasse liquide décrit précédemment selon l'invention, un polymère additionnel tel qu'un polymère filmogène . Selon la présente invention, on entend par "polymère filmogène", un polymère apte à former à lui seul ou en présence d'un agent auxiliaire de filmification, un film continu et adhérent sur un support, notamment sur les matières kératiniques. Parmi les polymères filmogènes utilisables dans la composition de la présente invention, on peut citer les polymères synthétiques, de type radicalaire ou de type polycondensat, les polymères d'origine naturelle et leurs mélanges. Comme polymère filmogène, on peut citer en particulier les polymères acryliques, les polyuréthanes, les polyesters, les polyamides, les polyurées, les polymères cellulosiques comme la nitrocellulose.The composition may comprise, in addition to the polymer dispersed in the liquid fatty phase described above according to the invention, an additional polymer such as a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials. Among the film-forming polymers which can be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures. As film-forming polymer, mention may in particular be made of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.
La composition selon l'invention peut en outre comprendre une ou des matières colorantes choisies parmi les colorants hydrosolubles, et les matières colorantes pulvérulentes comme les pigments, les nacres, et les paillettes bien connues de l'homme du métier. Les matières colorantes peuvent être présentes, dans la composition, en une teneur allant de 0,01 % à 50 % en poids, par rapport au poids de la composition, de préférence de 0,01 % à 30 % en poids. Par pigments, il faut comprendre des particules de toute forme, blanches ou colorées, minérales ou organiques, insolubles dans le milieu physiologique, destinées à colorer la composition.The composition according to the invention may also comprise one or more coloring materials chosen from water-soluble dyes, and pulverulent coloring materials such as pigments, nacres and flakes well known to those skilled in the art. The coloring matters can be present, in the composition, in a content ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight. The term “pigments” should be understood to mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.
Par nacres, il faut comprendre des particules de toute forme irisées, notamment produites par certains mollusques dans leur coquille ou bien synthétisées.By nacres, it is necessary to understand particles of any iridescent shape, in particular produced by certain molluscs in their shell or else synthesized.
Les pigments peuvent être blancs ou colorés, minéraux et/ou organiques. On peut citer, parmi les pigments minéraux, le dioxyde de titane, éventuellement traité en surface, les oxydes de zirconium ou de cérium, ainsi que les oxydes de zinc, de fer (noir, jaune ou rouge) ou de chrome, le violet de manganèse, le bleu outremer, l'hydrate de chrome et le bleu ferrique, les poudres métalliques comme la poudre d'aluminium, la poudre de cuivre. Parmi les pigments organiques, on peut citer le noir de carbone, les pigments de type D & C, et les laques à base de carmin de cochenille, de baryum, strontium, calcium, aluminium.The pigments can be white or colored, mineral and / or organic. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder. Among the organic pigments, mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
On peut également citer les pigments à effet tels les particules comportant un substrat organique ou minéral, naturel ou synthétique, par exemple le verre, les résines acrylique, le polyester, le polyuréthane, le polyethylene téréphtalate, les céramiques ou les alumines, ledit substrat étant recouvert ou non de substances métalliques comme l'aluminium, l'or, l'argent, le platine, le cuivre, le bronze, ou d'oxydes métalliques comme le dioxyde de titane, l'oxyde de fer, l'oxyde de chrome et leurs mélanges.Mention may also be made of effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being whether or not covered with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metallic oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures.
Les pigments nacrés peuvent être choisis parmi les pigments nacrés blancs tels que le mica recouvert de titane, ou d'oxychlorure de bismuth, les pigments nacrés colorés tels que le mica titane recouvert avec des oxydes de fer, le mica titane recouvert avec notamment du bleu ferrique ou de l'oxyde de chrome, le mica titane recouvert avec un pigment organique du type précité ainsi que les pigments nacrés à base d'oxychlorure de bismuth. . On peut également utiliser les pigments interferentiels, notamment à cristaux liquides ou multicouches.The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, mica titanium coated with in particular blue ferric or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on oxychloride bismuth. . Interferential pigments can also be used, in particular with liquid crystals or multilayers.
En particulier, il a été constaté que l'utilisation de la dispersion de particules d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide, telle que décrite précédemment, dans une composition cosmétique comprenant des matières colorantes pulvérulentes, en particulier des pigments, permet une bonne dispersion desdits pigments (sans sédimentation) et donc une bonne stabilité et une bonne homogénéité de la couleur dans le temps de la composition selon l'invention.In particular, it has been found that the use of the dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase, as described above, in a cosmetic composition comprising pulverulent coloring materials, in particular pigments, allows good dispersion of said pigments (without sedimentation) and therefore good stability and good color homogeneity over time of the composition according to the invention.
C'est pourquoi un objet de la présente invention est une composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, une dispersion de particules d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide et une matière colorante pulvérulente, notamment sous forme de pigments.This is why an object of the present invention is a cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase and a pulverulent coloring matter, in particular in the form of pigments. .
Les colorants liposolubles sont par exemple le rouge Soudan, le D&C Red 17, le D&C Green 6, le β-carotène, l'huile de soja, le brun Soudan, le D&C Yellow 11 , le D&C Violet 2, le D&C orange 5, le jaune quinoleine, le rocou. Les colorants hydrosolubles sont par exemple le jus de betterave, le bleu de méthylène, le sel disodique de ponceau, le sel disodique du vert d'alizarine, le jaune de quinoleine, le sel trisodique d'amarante, le sel disodique de tartrazine, le sel monosodique de rhodamine, le sel disodique de fuchsine, la xanthophylle.The liposoluble dyes are for example Sudan red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C orange 5, quinoleine yellow, annatto. The water-soluble dyes are, for example, beet juice, methylene blue, disodium salt of culvert, disodium salt of alizarin green, quinole yellow, trisodium salt of amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, disodium salt of fuchsin, xanthophyll.
La composition selon l'invention peut comprendre au moins une charge, notamment en une teneur allant de 0,01 % à 50 % en poids, par rapport au poids total de la composition, de préférence allant de 0,01 % à 30 % en poids. Par charges, il faut comprendre des particules de toute forme, incolores ou blanches, minérales ou de synthèse, insolubles dans le milieu de la composition quelle que soit la température à laquelle la composition est fabriquée. Ces charges servent notamment à modifier la rhéologie ou la texture de la composition.The composition according to the invention may comprise at least one filler, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. weight. By fillers, it is necessary to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the middle of the composition regardless of the temperature at which the composition is produced. These charges are used in particular to modify the rheology or the texture of the composition.
Les charges peuvent être minérales ou organiques de toute forme, plaquettaires, sphériques ou oblongues, quelle que soit la forme cristallographique ( par exemple feuillet, cubique, hexagonale, orthorombique, etc). On peut citer le talc, le mica, la silice, le kaolin, les poudres de polyamide (Nylon®) (Orgasol® de chez Atochem), de poly-β- alanine et de polyethylene, les poudres de polymères de tétrafluoroéthylène (Téflon®), la lauroyl-lysine, l'amidon, le nitrure de bore, les microsphères creuses polymériques expansées telles que celles de chlorure de polyvinylidene/acrylonitrile comme l'Expancel® (Nobel Industrie), de copolymères d'acide acrylique (Polytrap® de la sociétéThe fillers can be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) (Orgasol® from Atochem), poly-β-alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon®) ), lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), of acrylic acid copolymers (Polytrap® of the society
Dow Corning) et les microbilles de résine de silicone (Tospearls® de Toshiba, par exemple), les particules de polyorganosiloxanes élastomères, le carbonate de calcium précipité, le carbonate et l'hydro-carbonate de magnésium, l'hydroxyapatite, les microsphères de silice creuses (Silica Beads® de Maprecos), les microcapsules de verre ou de céramique, les savons métalliques dérivés d'acides organiques carboxyliques ayant de 8 à 22 atomes de carbone, de préférence de 12 à 18 atomes de carbone, par exemple le stéarate de zinc, de magnésium ou de lithium, le laurate de zinc, le myristate de magnésium.Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro carbonate, hydroxyapatite, microspheres hollow silica (Silica Beads® by Maprecos), glass or ceramic microcapsules, metallic soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example stearate zinc, magnesium or lithium, zinc laurate, magnesium myristate.
La composition selon l'invention peut également contenir des ingrédients couramment utilisés en cosmétique, tels que les vitamines, les épaississants, les gélifiants, les oligoéléments, les adoucissants, les séquestrants, les parfums, les agents alcalinisants ou acidifiants, les conservateurs, les filtres solaires, les tensioactifs, les anti-oxydants, les fibres, les agents anti-chutes des cheveux, les agents de soin du cil, les agents antipelliculaires, les agents propulseurs, ou leurs mélanges. Par "fibre", il faut comprendre un objet de longueur L et de diamètre D tel que L soit très supérieur à D, D étant le diamètre du cercle dans lequel s'inscrit la section de la fibre. En particulier, le rapport L/D (ou facteur de forme) est choisi dans la gamme allant de 3,5 àThe composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, filters sunscreen, surfactants, antioxidants, fibers, anti-hair loss agents, eyelash care agents, dandruff agents, propellants, or mixtures thereof. By "fiber" is meant an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed. In particular, the L / D ratio (or form factor) is chosen from the range going from 3.5 to
2500, de préférence de 5 à 500, et mieux de 5 à 150.2500, preferably from 5 to 500, and better still from 5 to 150.
En particulier, les fibres ont une longueur allant de 1 μm à 10 mm, de préférence de 0,1 mm à 5 mm et mieux de 0,3 mm à 3mm .In particular, the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm.
Les fibres utilisables dans la composition de l'invention peuvent être choisies parmi les fibres rigides ou non rigides, elles peuvent être d'origine synthétique ou naturelle, minérale ou organique. A titre de fibres utilisables dans la composition selon l'invention, on peut citer les fibres non rigides telles que les fibres de polyamide (Nylon®) ou les fibres rigides telles que les fibres de polyimide-amide comme celles vendues sous les dénomination "KERMEL", "The fibers which can be used in the composition of the invention can be chosen from rigid or non-rigid fibers, they can be of synthetic or natural, mineral or organic origin. As a usable fibers in the composition according to the invention, mention may be made of non-rigid fibers such as polyamide fibers (Nylon ®) or rigid fibers such as polyimide-amide fibers such as those sold under the trademark "KERMEL ","
KERMEL TECH" par la société RHODIA ou de poly-(p-phénylène-téréphtalamide) (ou d'aramide) notamment vendues sous la dénomination Kevlar ® par la société DUPONTKERMEL TECH "by the company RHODIA or poly- (p-phenylene-terephthalamide) (or aramid) especially sold under the name Kevlar ® by the company DUPONT
DE NEMOURS.FROM NEMOURS.
Les fibres peuvent être présentes dans la composition selon l'invention en une teneur allant de 0,1 à 10% en poids, mieux de 0,5 à 5% en poids par rapport au poids total de la composition.The fibers may be present in the composition according to the invention in a content ranging from 0.1 to 10% by weight, better still from 0.5 to 5% by weight relative to the total weight of the composition.
Les gélifiants utilisables dans les compositions selon l'invention peuvent être des gélifiant hydrophiles, lipophiles, organiques ou minéraux, polymériques ou moléculaires.The gelling agents which can be used in the compositions according to the invention can be hydrophilic, lipophilic, organic or inorganic, polymeric or molecular gelling agents.
Comme gélifiant lipophile minéral, on peut citer les argiles éventuellement modifiées comme les hectorites modifiées par un chlorure d'ammonium d'acide gras en C-io à C22, comme l'hectorite modifiée par du chlorure de di-stéaryl di-méthyl ammonium telle que, par exemple, celle commercialisée sous la dénomination de « Bentone 38V® » par la société ELEMENTIS.As mineral lipophilic gelling agent, mention may be made of clays optionally modified, such as hectorites modified with ammonium chloride of C 10 to C 22 fatty acid, such as hectorite modified with di-stearyl di-methyl ammonium chloride. such as, for example, that marketed under the name of "Bentone 38V ® " by the company ELEMENTIS.
On peut également citer la silice pyrogénee éventuellement traitée hydrophobe en surface dont la taille des particules est inférieure à 1 μm. Il est en effet possible de modifier chimiquement la surface de la silice, par réaction chimique générant une diminution du nombre de groupes silanol présents à la surface de la silice. On peut notamment substituer des groupes silanol par des groupements hydrophobes : on obtient alors une silice hydrophobe. Les groupements hydrophobes peuvent être :Mention may also be made of pyrogenic silica, optionally treated hydrophobically at the surface, the particle size of which is less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups can be:
- des groupements triméthylsiloxyle, qui sont notamment obtenus par traitement de silice pyrogénee en présence de l'hexaméthyldisilazane. Des silices ainsi traitées sont dénommées « Silica silylate » selon le CTFA (6eme édition, 1995). Elles sont par exemple commercialisées sous les références « Aerosil R812® » par la société DEGUSSA, « CAB-O-SIL TS-530®» par la société CABOT,- Trimethylsiloxyl groups, which are obtained in particular by treatment of pyrogenic silica in the presence of hexamethyldisilazane. Silicas thus treated are named "Silica Silylate" according to the CTFA (6 th edition, 1995). They are for example marketed under the references "Aerosil R812 ® " by the company DEGUSSA, "CAB-O-SIL TS-530 ® " by the company CABOT,
- des groupements diméthylsilyloxyle ou polydiméthylsiloxane, qui sont notamment obtenus par traitement de silice pyrogénee en présence de polydiméthylsiloxane ou du diméthyldichlorosilane. Des silices ainsi traitées sont dénommées « Silica diméthyl silylate » selon le CTFA (6eme édition, 1995). Elles sont par exemple commercialisées sous les références « Aerosil R972® », et « Aerosil R974® » par la société DEGUSSA, « CAB-O-SIL TS-610® » et « CAB-O-SIL TS-720® » par la société CABOT.- Dimethylsilyloxyl or polydimethylsiloxane groups, which are in particular obtained by treatment of pyrogenic silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (6 th edition, 1995). They are for example marketed under the references "Aerosil R972 ® ", and "Aerosil R974 ® " by the company DEGUSSA, "CAB-O-SIL TS-610 ® " and "CAB-O-SIL TS-720 ® " by the CABOT company.
La silice pyrogénee hydrophobe présente en particulier une taille de particules pouvant être nanométrique à micrométrique, par exemple allant d'environ de 5 à 200 nm.The hydrophobic pyrogenic silica has in particular a particle size which can be nanometric to micrometric, for example ranging from approximately 5 to 200 nm.
Les gélifiants lipophiles organiques polymériques sont par exemple les organopolysiloxanes élastomériques partiellement ou totalement réticulés, de structure tridimensionnelle, comme ceux commercialisés sous les dénominations de « KSG6® », « KSG16® » et de « KSG18® » par la société SHIN-ETSU, de « Trefil E-505C® » et « Trefil E-506C® » par la société DOW-CORNING, de « Gransil SR-CYC® », « SRThe polymeric organic lipophilic gelling agents are, for example, elastomeric polyorganosiloxanes partially or totally crosslinked, three-dimensional structure, such as those sold under the names "KSG6 ®", "KSG16 ®" and "KSG18 ®" by the company Shin-Etsu, for "Trefil E-505C ® " and "Trefil E-506C ® " by the company DOW-CORNING, from "Gransil SR-CYC ® ", "SR
DMF10® », « SR-DC556® », « SR 5CYC gel® », « SR DMF 10 gel® » et de « SR DC 556 gel® » par la société GRANT INDUSTRIES, de « SF 1204® » et de « JK 113® » par la société GENERAL ELECTRIC ; l'éthylcellulose comme celle vendue sous la dénomination d'« Ethocel® » par la société DOW CHEMICAL ; les galactommananes comportant de un à six, et en particulier de deux à quatre, groupes hydroxyle par ose, substitués par une chaîne alkyle saturée ou non, comme la gomme de guar alkylée par des chaînes alkyle en C-\ à C6, et en particulier en d à C3 et leurs mélanges. Les copolymères séquences de type « dibloc » ou « tribloc » du type polystyrène/polyisoprène, polystyrène/polybutadiene tels que ceux commercialisés sous la dénomination de « Luvitol HSB® » par la société BASF, du type polystyrène/copoly(éthylène-propylène) tels que ceux commercialisés sous la dénomination de « Kraton® » par la société SHELL CHEMICAL CO ou encore du type polystyrène/copoly(éthylène-butylène).DMF10 ® "," SR-DC556 ® "," SR 5CYC gel ® "," SR DMF 10 gel ® "and" SR DC 556 gel ® "by GRANT INDUSTRIES," SF 1204 ® "and" JK 113 ® ”by GENERAL ELECTRIC; ethyl cellulose such as that sold under the name of "Ethocel ®" by the company Dow Chemical; galactomannans comprising from one to six, particularly two to four hydroxyl groups per saccharide, substituted with a saturated alkyl chain or not, such as guar gum alkylated with alkyl chains of C \ to C 6, and in particular in d to C 3 and their mixtures. The block copolymers of "diblock" or "triblock" of the polystyrene / polyisoprene or polystyrene / polybutadiene type such as those marketed under the name "Luvitol HSB ®" by the company BASF, of the polystyrene / copoly (ethylene-propylene) type such as those sold under the name "Kraton ®" by Shell Chemical Co., or the polystyrene / copoly (ethylene-butylene).
Parmi les gélifiants lipophiles pouvant être utilisés dans les compositions selon l'invention, on peut encore citer les esters de dextrine et d'acide gras, tels que les palmitates de dextrine, notamment tels que ceux commercialisés sous les dénominations de « Rheopearl TL® » ou « Rheopearl KL® » par la société CHIBA FLOUR.Among the lipophilic gelling agents which can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those marketed under the names of "Rheopearl TL ® " or "Rheopearl KL ® " by the company CHIBA FLOUR.
Les gélifiants lipophiles peuvent être présents dans la composition selon l'invention en une teneur allant de 0,05 à 40% en poids par rapport au poids total de la composition, de préférence de 0,5 à 20% et mieux de 1 à 15% en poids.The lipophilic gelling agents can be present in the composition according to the invention in a content ranging from 0.05 to 40% by weight relative to the total weight of the composition, preferably from 0.5 to 20% and better still from 1 to 15 % in weight.
Comme gélifiant hydrophile ou hydrosolubles, on peut citer : les homo- ou copolymères d'acides acrylique ou méthacrylique ou leurs sels et leurs esters et en particulier les produits vendus sous les dénominations « VERSICOL F »ou « VERSICOL K » par la société ALLIED COLLOID,As hydrophilic or water-soluble gelling agents, mention may be made of: homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the names "VERSICOL F" or "VERSICOL K" by the company ALLIED COLLOID,
« UTRAHOLD 8 » par la société CIBA-GEIGY, les acides polyacryliques de type"UTRAHOLD 8" by the company CIBA-GEIGY, polyacrylic acids of the type
SYNTHALEN K, les copolymères d'acide acrylique et d'acrylamide vendus sous la forme de leur sel de sodium sous les dénominations « RETEN » par la société HERCULES, le polyméthacrylate de sodium vendu sous la dénomination « DARVAN N°7 » par la société VANDERBILT, les sels de sodium d'acides polyhydroxycarboxyliques vendus sous la dénomination « HYDAGEN F » par la société HENKEL, les copolymères acide polyacryliques/acrylates d'alkyle de type PEMULEN, l'AMPS (Acide polyacrylamidométhyl propane sulfonique neutralisé partiellement à l'ammoniaque et hautement réticulé) commercialisé par la société CLARIANT,SYNTHALEN K, the copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names "RETEN" by the company HERCULES, the sodium polymethacrylate sold under the name "DARVAN N ° 7" by the company VANDERBILT, the sodium salts of polyhydroxycarboxylic acids sold under the name "HYDAGEN F" by the company HENKEL, the polyacrylic acid / alkyl acrylate copolymers of the PEMULEN type, AMPS (Polyacrylamidomethyl propane sulfonic acid partially neutralized with ammonia and highly crosslinked) sold by the company CLARIANT,
- les copolymères AMPS/acrylamide de type SEPIGEL ou SIMULGEL commercialisés par la société SEPPIC, et les copolymères AMPS/méthacrylates d'alkyle polyoxyéthylénés (réticulés ou non) et leurs mélanges.- the AMPS / acrylamide copolymers of the SEPIGEL or SIMULGEL type sold by the company SEPPIC, and the AMPS / methacrylate copolymers of polyoxyethylenated alkyl (crosslinked or not) and their mixtures.
Comme autres exemples de polymères gélifiants hydrosolubles, on peut citer : - les protéines comme les protéines d'origine végétale telles que les protéines de blé, de soja ; les protéines d'origine animale tels que les kératines, par exemples les hydrolysats de kératine et les kératines sulfoniques ; les polymères de chitine ou de chitosane anioniques, cationiques, amphotères ou non-ioniques ; les polymères de cellulose tels que Phydroxyéthylcellulose, l'hydroxypropylcellulose, la méthylcellulose, l'éthylhydroxyéthylcellulose, la carboxyméthylcellulose, ainsi que les dérivés quaternisés de la cellulose ; les polymères vinyliques, comme les polyvinylpyrrolidones, les copolymères de l'éther méthylvinylique et de l'anhydride malique, le copolymère de l'acétate de vinyle et de l'acide crotonique, les copolymères de vinylpyrrolidone et d'acétate de vinyle ; les copolymères de vinylpyrrolidone et de caprolactame ; l'alcool polyvinylique; les polyuréthanes associatifs tels que le polymère C16-OE120-C16 de la société SERVO DELDEN (commercialisé sous le nom SER AD FX1100, molécule à fonction uréthanne et poids moléculaire moyen en poids de 1300), OE étant un motif oxyéthyléné, le Rhéolate 205 à fonction urée vendu par la société RHEOX ou encore le Rhéolate 208 ou 204 (ces polymères étant vensus sous forme pure) ou le DW 1206B de chez RHOM & HAAS à chaîne alkyle en C20 et à liaison uréthane, vendu à 20 % en matière sèche dans l'eau. On peut aussi utiliser des solutions ou dispersions de ces polyuréthanes- associatifs notamment dans l'eau ou en milieu hydroalcoolique. A titre d'exemple, de tels polymères on peut citer, le SER AD FX1010, le SER AD FX1035 et leAs other examples of water-soluble gelling polymers, mention may be made of: - proteins such as proteins of plant origin such as wheat, soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as quaternized derivatives of cellulose; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; vinylpyrrolidone and caprolactam copolymers; polyvinyl alcohol; associative polyurethanes such as the polymer C 16 -OE 120 -C 16 from the company SERVO DELDEN (marketed under the name SER AD FX1100, molecule with urethane function and average molecular weight by weight of 1300), OE being an oxyethylenated unit, the Rheolate 205 with urea function sold by the company RHEOX or even Rheolate 208 or 204 (these polymers being vensus in pure form) or DW 1206B from RHOM & HAAS with C 20 alkyl chain and urethane bond, sold at 20% as dry matter in water. It is also possible to use solutions or dispersions of these associative polyurethanes, in particular in water or in an alcoholic medium. By way of example, such polymers that may be mentioned include SER AD FX1010, SER AD FX1035 and
SER AD 1070 de la société SERVO DELDEN, le Rhéolate 255, le Rhéolate 278 et leSER AD 1070 from SERVO DELDEN, Rheolate 255, Rheolate 278 and
Rhéolate 244 vendus par la société RHEOX. On peut aussi utiliser le produit DW 1206F et le DW 1206J, ainsi que l'Acrysol RM 184 ou l'Acrysol 44 de la société RHOM & HAAS, ou bien encore le Borchigel LW 44 de la société BORCHERS, les polymères d'origine naturelle, éventuellement modifiés, tels que : - les gommes arabiques, la gomme de guar, les dérivés du xanthane, la gomme de karaya ; les alginates et les carraghénanes ; les glycoaminoglycanes, l'acide hyaluronique et ses dérivés ; la résine shellac, la gomme de sandaraque, les dammars, les élémis, les copals ; l'acide désoxyribonucléïque ; les muccopolysaccharides tels que l'acide hyaluronique, les chondroïtines sulfate, et leurs mélanges.Rheolate 244 sold by the company RHEOX. One can also use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from the company RHOM & HAAS, or even Borchigel LW 44 from the company BORCHERS, polymers of natural origin , possibly modified, such as: - gum arabic, guar gum, xanthan derivatives, karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; shellac resin, sandara gum, dammars, elemis, copals; deoxyribonucleic acid; muccopolysaccharides such as hyaluronic acid, chondroitins sulfate, and mixtures thereof.
Les gélifiants hydrophiles peuvent être présents dans la composition selon l'invention en une teneur allant de 0,05 à 20% en poids par rapport au poids total de la composition, de préférence de 0,5 à 10% et mieux de 0,8 à 5% en poids.The hydrophilic gelling agents can be present in the composition according to the invention in a content ranging from 0.05 to 20% by weight relative to the total weight of the composition, preferably from 0.5 to 10% and better still from 0.8 at 5% by weight.
La composition selon l'invention peut contenir des agents tensioactifs émulsionnants présents notamment en une proportion allant de 0,5 à 30 % en poids par rapport au poids total de la composition, mieux de 2 à 15% et mieux de 3 à 10 %. Ces agents tensioactifs peuvent être choisis parmi des agents tensioactifs anioniques, cationiques ou non ioniques. On peut se reporter au document « Encyclopedia of Chemical Technology, KIRK-OTHMER », volume 22, p.333-432, 3ème édition, 1979, WILEY, pour la définition des propriétés et des fonctions (émulsionnant) des tensioactifs, en particulier p.347-377 de cette référence, pour les tensioactifs anioniques et non-ioniques.The composition according to the invention may contain emulsifying surfactants present in particular in a proportion ranging from 0.5 to 30% by weight relative to the total weight of the composition, better from 2 to 15% and better still from 3 to 10%. These surfactants can be chosen from anionic, cationic or nonionic surfactants. Reference may be made to the document “Encyclopedia of Chemical Technology, KIRK-OTHMER”, volume 22, p.333-432, 3rd edition, 1979, WILEY, for the definition of the properties and functions (emulsifier) of surfactants, in particular p .347-377 of this reference, for anionic and nonionic surfactants.
Les tensioactifs utilisés préférentiellement dans la composition selon l'invention sont choisis parmi : a) les agents tensioactifs non ioniques de HLB supérieur ou égal à 8 à 25 °C, utilisés seuls ou en mélange; on peut citer notamment : les éthers oxyéthylénés et/ou oxypropylénés (pouvant comporter de 1 à 150 groupes oxyéthylénés et/ou oxypropylénés) de glycérol ; les éthers oxyéthylénés et/ou oxypropylénés (pouvant comporter de 1 à 150 groupes oxyéthylénés et/ou oxypropylénés) d'alcools gras (notamment d'alcool en C8-C24, et de préférence en C12-C18) tels que l'éther oxyéthyléné de l'alcool cétéarylique à 30 groupes oxyéthylénés (nom CTFA "Ceteareth-30 ") et l'éther oxyéthyléné du mélange d'alcools gras en C12-C15 comportant 7 groupes oxyéthylénés (nom CTFA "C12-15 Pareth-7" commercialisé sous la dénomination « NEODOL 25-7 »® par SHELL CHEMICALS ; les esters d'acide gras (notamment d'acide en C8-C24, et de préférence en C16-C22) et de polyethylene glycol (pouvant comprendre de 1 à 150 motifs d'éthylèneglycol) tels que le stéarate de PEG-50 et le monostéarate de PEG-40 commercialisé sous le nom MYRJ 52P par la société ICI UNIQUEMA; les esters d'acide gras (notamment d'acide en C8-C24, et de préférence en C16-C22) et des éthers de glycérol oxyéthylénés et/ou oxypropylénés (pouvant comporter de 1 à 150 groupes oxyéthylénés et/ou oxypropylénés), comme le monostéarate de PEG-200 glyceryle vendu sous la dénomination « Simulsol 220 TM » par la société SEPPIC ; le stéarate de glyceryle polyéthoxylé à 30 groupes d'oxyde d'éthylène comme le produit TAGAT S vendu par la société GOLDSCHMIDT, l'oléate de glyceryle polyéthoxylé à 30 groupes d'oxyde d'éthylène comme le produit TAGAT O vendu par la société GOLDSCHMIDT, le cocoate de glyceryle polyéthoxylé à 30 groupes d'oxyde d'éthylène comme le produit VARIONIC Ll 13 vendu par la société SHEREX, l'isostéarate de glyceryle polyéthoxylé à 30 groupes d'oxyde d'éthylène comme le produit TAGAT L vendu par la société GOLDSCHMIDT et le laurate de glyceryle polyéthoxylé à 30 groupes d'oxyde d'éthylène comme le produit TAGAT I de la société GOLDSCHMIDT ; les esters d'acide gras (notamment d'acide en C8-C24, et de préférence en C16-C22) et des éthers de sorbitol oxyéthylénés et/ou oxypropylénés (pouvant comporter de 1 à 150 groupes oxyéthylénés et/ou oxypropylénés), comme le polysorbate 60 vendu sous la dénomination « Tween 60 » par la société UNIQUEMA ; la diméthicone copolyol, telle que celle vendue sous la dénomination « Q2-5220 » par la société DOW CORNING ; la diméthicone copolyol benzoate (FINSOLV SLB 101 et 201 de la société FINTEX) ; les copolymères d'oxyde propylène et d'oxyde d'éthylène, également appelés polycondensats OE/Opcomme par exemple les polycondensats tribloc polyethylene glycol / polypropylène glycol / polyethylene glycol vendus sous les dénominations "SYNPERONIC" comme les "SYNPERONIC PE/ L44" et "SYNPERONICThe surfactants preferably used in the composition according to the invention are chosen from: a) nonionic surfactants with an HLB greater than or equal to 8 at 25 ° C., used alone or as a mixture; mention may in particular be made of: oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of glycerol; oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular C8-C24, and preferably C12-C18 alcohol) such as oxyethylenated ether cetearyl alcohol with 30 oxyethylenated groups (CTFA name "Ceteareth-30") and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols comprising 7 oxyethylenated groups (CTFA name "C12-15 Pareth-7" marketed under the name "NEODOL 25-7" ® by SHELL CHEMICALS; fatty acid esters (especially C8-C24, and preferably C16-C22) and polyethylene glycol (which may include from 1 to 150 units of ethylene glycol) such as PEG-50 stearate and PEG-40 monostearate sold under the name MYRJ 52P by the company ICI UNIQUEMA; fatty acid esters ( especially C8-C24 acid, and preferably C16-C22) and oxyethylenated and / or oxypropylenated glycerol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups), such as PEG-200 glyceryl monostearate sold under the name “Simulsol 220 TM” by the company SEPPIC, glyceryl stearate polyethoxylated with 30 ethylene oxide groups such as the product TAGAT S sold by the company GOLDSCHMIDT, polyethoxylated glyceryl oleate with 30 groups of ethylene oxide as the TAGAT O product sold by pa r the company GOLDSCHMIDT, the polyethoxylated glyceryl cocoate with 30 ethylene oxide groups such as the product VARIONIC Ll 13 sold by the company SHEREX, the polyethoxylated glyceryl isostearate with 30 ethylene oxide groups such as the product TAGAT L sold by the company GOLDSCHMIDT and glyceryl laurate polyethoxylated with 30 ethylene oxide groups as the product TAGAT I from the company GOLDSCHMIDT; fatty acid esters (especially C8-C24, and preferably C16-C22 acid) and oxyethylenated and / or oxypropylenated sorbitol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups), such as polysorbate 60 sold under the name "Tween 60" by the company UNIQUEMA; dimethicone copolyol, such as that sold under the name "Q2-5220" by the company DOW CORNING; dimethicone copolyol benzoate (FINSOLV SLB 101 and 201 from FINTEX); copolymers of propylene oxide and ethylene oxide, also called OE / Op polycondensates such as polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates sold under the names "SYNPERONIC" such as "SYNPERONIC PE / L44" and "SYNPERONIC
PE/F127 " par la société ICI, et leurs mélanges. et leurs mélanges, b) les agents tensioactif non ioniques de HLB inférieur à 8 à 25 °C, éventuellement associés à un ou plusieurs agents tensioactif non ioniques de HLB supérieur à 8 à 25 °C, tels que cités ci-dessus tels que : les esters et éthers d'osés tels que les stéarate de sucrose, cocoate de sucrose, stéarate de sorbitan et leurs mélanges comme l'Ariatone 2121 commercialisé par la société ICI ; les esters d'acides gras (notamment d'acide en C8-C24, et de préférence en C16-C22) et de polyol, notamment de glycérol ou de sorbitol, tels que stéarate de glyceryle, stéarate de glyceryle tel que le produit vendu sous la dénomination TEGIN M par la société GOLDSCHMIDT, laurate de glyceryle tel que le produit vendu sous la dénomination IMWITOR 312 par la société HULS, stéarate de polyglycéryl-2, tristéarate de sorbitan, ricinoléate de glyceryle ; le mélange de cyclométhicone/diméthicone copolyol vendu sous la dénomination "Q2-3225C" par la société DOW CORNING. c) Les tensioactifs anioniques tels que : les sels d'acides gras en C16-C30 notamment ceux dérivant des aminés, comme le stéarate de triéthanolamine; les sels d'acides gras polyoxyéthylénés notamment ceux dérivant des aminés ou les sels alcalins, et leurs mélanges ; les esters phosphoriques et leurs sels tels que le "DEA oleth-10 phosphate" (Crodafos N 10N de la société CRODA) ; les sulfosuccinates tels que le "Disodium PEG-5 citrate lauryl sulfosuccinate" et le "Disodium ricinoleamido MEA sulfosuccinate" les alkylethersulfat.es tels que le lauryl éther sulfate de sodium ; les iséthionates ; les acylglutamates tels que le "Disodium hydrogenated tallow glutamate"PE / F127 "by the company ICI, and their mixtures. And their mixtures, b) nonionic surfactants with an HLB of less than 8 at 25 ° C., optionally combined with one or more nonionic surfactants with an HLB of more than 8 to 25 ° C. 25 ° C, as mentioned above such as: esters and ethers of dares such as sucrose stearate, sucrose cocoate, sorbitan stearate and their mixtures such as Ariatone 2121 sold by the company ICI; esters fatty acids (in particular C8-C24, and preferably C16-C22) and polyol, in particular glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name TEGIN M by the company GOLDSCHMIDT, glyceryl laurate such as the product sold under the name IMWITOR 312 by the company HULS, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate; the mixture of cyclomethicone / dimethicone copolyol v coated under the name "Q2-3225C" by the company DOW CORNING. c) Anionic surfactants such as: the salts of C 16 -C 30 fatty acids, in particular those derived from amines, such as triethanolamine stearate; the salts of polyoxyethylenated fatty acids, in particular those derived from amines or the alkaline salts, and their mixtures; phosphoric esters and their salts such as "DEA oleth-10 phosphate" (Crodafos N 10N from the company CRODA); sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate" alkyl ether sulfates, such as sodium lauryl ether sulfate; isethionates; acylglutamates such as "Disodium hydrogenated tallow glutamate"
(AMISOFT HS-21 R commercialisé par la société AJINOMOTO) et leurs mélanges.(AMISOFT HS-21 R sold by the company AJINOMOTO) and their mixtures.
Convient tout particulièrement à l'invention, le stéarate de triéthanolamine. Ce dernier est généralement obtenu par simple mélange de l'acide stéarique et de la triéthanolamine.Particularly suitable for the invention, triethanolamine stearate. The latter is generally obtained by simple mixing of stearic acid and triethanolamine.
On utilise de préférence des tensioactifs permettant l'obtention d'emulsion huile-dans-eau ou cire-dans-eau.Surfactants are preferably used which make it possible to obtain an oil-in-water or wax-in-water emulsion.
Bien entendu, l'homme du métier veillera à choisir ce ou ces éventuels composés complémentaires, et/ou leur quantité, de manière telle que les propriétés avantageuses de la composition correspondante selon l'invention ne soient pas, ou substantiellement pas, altérées par l'adjonction envisagée.Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the corresponding composition according to the invention are not, or not substantially, affected by the planned addition.
La composition selon l'invention peut comprendre un milieu aqueux, constituant une phase aqueuse, qui peut former la phase continue de la composition.The composition according to the invention can comprise an aqueous medium, constituting an aqueous phase, which can form the continuous phase of the composition.
La phase aqueuse peut être constituée essentiellement d'eau ; elle peut également comprendre un mélange d'eau et de solvant miscible à l'eau (miscibilité dans l'eau supérieure à 50 % en poids à 25 °C) comme les monoalcools inférieurs ayant de 1 à 5 atomes de carbone tels que l'éthanol, Pisopropanol, les glycols ayant de 2 à 8 atomes de carbone tels que le propylène glycol, l'éthylène glycol, le 1 ,3-butylène glycol, le dipropylène glycol, les cétones en C3-C4, les aldéhydes en C2-C4 ef |eur mélanges- La phase aqueuse (eau et éventuellement le solvant miscible à l'eau) peut être présente, en une teneur allant de 0,1 % à 95 % en poids, par rapport au poids total de la composition, de préférence allant de 1 % à 80 % en poidsThe aqueous phase can consist essentially of water; it can also comprise a mixture of water and water-miscible solvent (miscibility in water greater than 50% by weight at 25 ° C) such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol, Pisopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes e f | eur mixes- The aqueous phase (water and optionally the water-miscible solvent) may be present, in a content ranging from 0.1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 1% to 80% by weight
La composition selon l'invention peut se présenter notamment sous forme de suspension, de dispersion, de solution, de gel, d'emulsion, notamment émulsion huile-dans-eau (H/E) ou eau-dans-huile (E/H), ou multiple (E/H/E ou polyol/H/E ou H/E/H), sous forme de crème, de pâte, de mousse, de dispersion de vésicules notamment de lipides ioniques ou non, de lotion biphasé ou multiphase, de spray, de poudre, de pâte, notamment de pâte souple (notamment de pâte ayant de viscosité dynamique à 25°C de l'ordre de 0,1 à 40 Pa.s sous une vitesse de cisaillement de 200 s"1, après 10 minutes de mesure en géométrie cône/plan). La composition peut être anhydre, par exemple il peut s'agir d'une pâte ou d'une stick anhydre. La composition peut être une composition non rincée.The composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of two-phase lotion or multiphase, spray, powder, paste, in particular flexible paste (in particular paste having a dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s under a shear speed of 200 s "1 , after 10 minutes of measurement in cone / plane geometry). The composition can be anhydrous, for example it can be an anhydrous paste or stick. The composition can be a leave-in composition.
L'homme du métier pourra choisir la forme galénique appropriée, ainsi que sa méthode de préparation, sur la base de ses connaissances générales, en tenant compte d'une part de la nature des constituants utilisés, notamment de leur solubilité dans le support, et d'autre part de l'application envisagée pour la composition.Those skilled in the art can choose the appropriate dosage form, as well as its method of preparation, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand of the application envisaged for the composition.
Selon un autre aspect, l'invention concerne également un ensemble cosmétique comprenant : i) un récipient délimitant au moins un compartiment, ledit récipient étant fermé par un élément de fermeture ; et ii) une composition disposée à l'intérieur dudit compartiment, la composition étant conforme à l'une quelconque des revendications qui précèdent. Le récipient peut être sous toute forme adéquate. Il peut être notamment sous forme d'un flacon, d'un tube, d'un pot, d'un étui, d'une boite, d'un sachet ou d'un boîtier.According to another aspect, the invention also relates to a cosmetic assembly comprising: i) a container delimiting at least one compartment, said container being closed by a closing element; and ii) a composition disposed inside said compartment, the composition being according to any one of the preceding claims. The container can be in any suitable form. It can in particular be in the form of a bottle, a tube, a pot, a case, a box, a sachet or a case.
L'élément de fermeture peut être sous forme d'un bouchon amovible, d'un couvercle, d'un opercule, d'une bande déchirable, ou d'une capsule, notamment du type comportant un corps fixé au récipient et une casquette articulée sur le corps. Il peut être également sous forme d'un élément assurant la fermeture sélective du récipient, notamment une pompe, une valve, ou un clapet.The closure element may be in the form of a removable stopper, a cover, a cover, a tearable strip, or a capsule, in particular of the type comprising a body fixed to the container and an articulated cap. on the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.
Le récipient peut être associé à un applicateur, notamment sous forme d'une brosse comportant un arrangement de poils maintenus par un fil torsadé. Une telle brosse torsadée est décrite notamment dans le brevet US 4 887 622. Il peut être également sous forme d'un peigne comportant une pluralité d'éléments d'application, obtenus notamment de moulage. De tels peignes sont décrits par exemple dans le brevet FR 2 796 529. L'applicateur peut être sous forme d'un pinceau, tel que décrit par exemple dans le brevet FR 2 722 380. L'applicateur peut être sous forme d'un bloc de mousse ou d'élastomère, d'un feutre, ou d'une spatule. L'applicateur peut être libre (houppette ou éponge) ou solidaire d'une tige portée par l'élément de fermeture, tel que décrit par exemple dans le brevet US 5 492 426. L'applicateur peut être solidaire du récipient, tel que décrit par exemple le brevet FR 2 761 959.The container can be associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Pat. No. 4,887,622. It can also be in the form of a comb comprising a plurality of application elements, obtained in particular by molding. Such combs are described for example in patent FR 2 796 529. The applicator can be in the form of a brush, as described for example in patent FR 2 722 380. The applicator can be in the form of a block of foam or elastomer, a felt, or a spatula. The applicator can be free (puff or sponge) or integral with a rod carried by the closure element, as described for example in US patent 5,492,426. The applicator can be integral with the container, as described for example the patent FR 2 761 959.
Le produit peut être contenu directement dans le récipient, ou indirectement. A titre d'exemple, le produit peut être disposé sur un support imprégné, notamment sous forme d'une lingette ou d'un tampon, et disposé (à l'unité ou plusieurs) dans une boîte ou dans un sachet. Un tel support incorporant le produit est décrit par exemple dans la demande WO 01/03538. L'élément de fermeture peut être couplé au récipient par vissage. Alternativement, le couplage entre l'élément de fermeture et le récipient se fait autrement que par vissage, notamment via un mécanisme à baïonnette, par encliquetage, serrage, soudage, collage, ou par attraction magnétique. Par "encliquetage" on entend en particulier tout système impliquant le franchissement d'un bourrelet ou d'un cordon de matière par déformation élastique d'une portion, notamment de l'élément de fermeture, puis par retour en position non contrainte élastiquement de ladite portion après le franchissement du bourrelet ou du cordon.The product can be contained directly in the container, or indirectly. For example, the product can be placed on an impregnated support, in particular in the form of a wipe or a tampon, and placed (individually or several) in a box or in a sachet. Such a support incorporating the product is described for example in application WO 01/03538. The closure element can be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, tightening, welding, bonding, or by magnetic attraction. By "snap-fastening" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the non-elastically constrained position of said portion after crossing the bead or cord.
Le récipient peut être au moins pour partie réalisé en matériau thermoplastique. A titre d'exemples de matériaux thermoplastiques, on peut citer le polypropylène ou le polyethylene.The container can be at least partly made of thermoplastic material. As examples of thermoplastic materials, mention may be made of polypropylene or polyethylene.
Alternativement, le récipient est réalisé en matériau non thermoplastique, notamment en verre ou en métal (ou alliage).Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).
Le récipient peut être à parois rigides ou à parois déformables, notamment sous forme d'un tube ou d'un flacon tube.The container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.
Le récipient peut comprendre des moyens destinés à provoquer ou faciliter la distribution de la composition. A titre d'exemple, le récipient peut être à parois déformables de manière à provoquer la sortie de la composition en réponse à une surpression à l'intérieur du récipient, laquelle surpression est provoquée par écrasement élastique (ou non élastique) des parois du récipient. Alternativement, notamment lorsque le produit est sous forme d'un stick, ce dernier peut être entraîné par un mécanisme à piston. Toujours dans le cas d'un stick, notamment de produit de maquillage (rouge à lèvres, fond de teint, etc.), le récipient peut comporter un mécanisme, notamment à crémaillère, ou avec une tige filetée, ou avec une rampe hélicoïdale, et apte à déplacer un stick en direction de ladite ouverture. Un tel mécanisme est décrit par exemple dans le brevet FR 2 806 273 ou dans le brevet FR 2 775 566. Un tel mécanisme pour un produit liquide est décrit dans le brevetThe container may include means for causing or facilitating the distribution of the composition. For example, the container may have deformable walls so as to cause the exit of the composition in response to an overpressure inside the container, which overpressure is caused by elastic (or inelastic) crushing of the walls of the container. . Alternatively, especially when the product is in the form of a stick, the latter can be driven by a piston mechanism. Still in the case of a stick, in particular of makeup product (lipstick, foundation, etc.), the container may include a mechanism, in particular rack and pinion, or with a threaded rod, or with a helical ramp, and able to move a stick in the direction of said opening. Such a mechanism is described for example in patent FR 2 806 273 or in patent FR 2 775 566. Such a mechanism for a liquid product is described in the patent
FR 2 727 609.FR 2,727,609.
Le récipient peut être constitué d'un boîtier avec un fond délimitant au moins un logement contenant la composition, et un couvercle, notamment articulé sur le fond, et apte à recouvrir au moins en partie ledit fond. Un tel boîtier est décrit par exemple dans la demande WO 03/018423 ou dans le brevet FR 2 791 042.The container may consist of a housing with a bottom delimiting at least one housing containing the composition, and a cover, in particular articulated on the bottom, and capable of covering said bottom at least in part. Such a case is described, for example, in application WO 03/018423 or in patent FR 2,791,042.
Le récipient peut être équipé d'un essoreur disposé au voisinage de l'ouverture du récipient. Un tel essoreur permet d'essuyer l'applicateur et éventuellement, la tige dont il peut être solidaire. Un tel essoreur est décrit par exemple dans le brevet FR 2 792 618.The container can be equipped with a wringer disposed near the opening of the container. Such a wringer makes it possible to wipe the applicator and possibly, the rod of which it may be integral. Such a wringer is described for example in patent FR 2 792 618.
La composition peut être à la pression atmosphérique à l'intérieur du récipient (à température ambiante) ou pressurisée, notamment au moyen d'un gaz propulseur (aérosol). Dans ce dernier cas, le récipient est équipé d'une valve (du type de celles utilisées pour les aérosols).The composition can be at atmospheric pressure inside the container (at room temperature) or pressurized, in particular by means of a propellant gas (aerosol). In the latter case, the container is fitted with a valve (of the type used for aerosols).
Le contenu des brevets ou demandes de brevets cités précédemment sont incorporés par référence dans la présente demande.The content of the patents or patent applications cited above are incorporated by reference into the present application.
L'invention est illustrée plus en détails par les exemples décrits ci-après.The invention is illustrated in more detail by the examples described below.
Exemples 1 et 2 : Préparation de dispersion de particules de polymèreExamples 1 and 2: Preparation of dispersion of polymer particles
Les exemples 1 et 2 illustrent la préparation de polymères conformes à l'invention, aptes à former une dispersion de particules dans un milieu organique considéré. Dans ces exemples, on détermine, après préparation de ladite dispersion, les masses molaires moyennes en poids (Mw) et en nombre (Mn) du polymère, la température de transition vitreuse du polymère, le taux de matière sèche (ou extrait sec) de la dispersion et la taille des particules de polymères.Examples 1 and 2 illustrate the preparation of polymers in accordance with the invention, capable of forming a dispersion of particles in an organic medium under consideration. In these examples, after preparation of said dispersion, the average molar masses by weight (Mw) and by number (Mn) of the polymer are determined, the glass transition temperature of the polymer, the dry matter (or dry extract) content of the dispersion and size of the polymer particles.
Les masses molaires moyennes en poids (Mw) et en nombre (Mn) sont déterminées par chromatographie liquide par perméation de gel (solvant THF, courbe d'étalonnage établie avec des étalons de polystyrène linéaire, détecteur réfractométrique).The average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
La mesure de la température de transition vitreuse (Tg) est effectuée selon la norme ASTM D3418-97, par analyse enthalpique différentielle (DSC "Differential Scanning Calorimetry") sur calorimètre, sur une plage de température comprise entre -100°C et +150°C à une vitesse de chauffe de 10°C/min dans des creusets en aluminium de 150 μl. La préparation des creusets se fait de la manière suivante : dans un creuset en aluminium de 150 μl on introduit 100 μl de la dispersion obtenue et on laisse le solvant s'évaporer pendant 24h à température ambiante et à 50% d'humidité relative. On renouvelle l'opération puis on introduit le creuset dans le calorimètre Mettler DSC30.The measurement of the glass transition temperature (Tg) is carried out according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range between -100 ° C and +150 ° C at a heating rate of 10 ° C / min in 150 μl aluminum crucibles. The crucibles are prepared as follows: 100 μl of the dispersion obtained is introduced into an aluminum crucible of 150 μl and the solvent is allowed to evaporate for 24 hours at room temperature and at 50% relative humidity. The operation is repeated and then the crucible is introduced into the Mettler DSC30 calorimeter.
Le taux de matière sèche (ou extrait sec), c'est à dire la teneur en matière non volatile, peut être mesurée de différentes manières : on peut citer par exemple les méthodes par séchage à l'étuve ou lés méthodes par séchage par exposition à un rayonnement infrarouge.The rate of dry matter (or dry extract), that is to say the content of non-volatile matter, can be measured in different ways: for example, the methods by drying in an oven or the methods by drying by exposure to infrared radiation.
De préférence, le taux de matière sèche de la dispersion de polymère obtenue est mesuré par échauffement de l'échantillon par des rayons infrarouges de 2 μm à 3,5 μm de longueur d'onde. Les substances contenues dans la composition qui possèdent une pression de vapeur élevée s'évaporent sous l'effet de ce rayonnement. La mesure de la perte de poids de l'échantillon permet de déterminer l'extrait sec de la composition. Ces mesures sont réalisées au moyen d'un dessiccateur à infrarouges commercial LP16 de chez Mettler. Cette technique est parfaitement décrite dans la documentation de l'appareil fournie par Mettler.Preferably, the dry matter content of the polymer dispersion obtained is measured by heating the sample by infrared rays from 2 μm to 3.5 μm in wavelength. The substances contained in the composition which have a high vapor pressure evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition. These measurements are carried out using a commercial infrared desiccator LP16 from Mettler. This technique is fully described in the device documentation provided by Mettler.
Le protocole de mesure est le suivant : on étale environ 1g de la dispersion sur une coupelle métallique. Celle-ci, après introduction dans le dessiccateur, est soumise à une consigne de température de 120°C pendant une heure. La masse humide de l'échantillon, correspondant à la masse initiale et la masse sèche de l'échantillon, correspondant à la masse après exposition au rayonnement, sont mesurées au moyen d'une balance de précision. Le taux de matière sèche est calculée de la manière suivante :The measurement protocol is as follows: approximately 1 g of the dispersion is spread over a metal dish. This, after introduction into the desiccator, is subjected to a temperature set point of 120 ° C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance. The dry matter content is calculated as follows:
Extrait Sec = 100 x (masse sèche / masse humide).Dry extract = 100 x (dry mass / wet mass).
Les tailles de particules peuvent être mesurées par différentes techniques : on peut citer en particulier les techniques de diffusion de la lumière (dynamiques et statiques), les méthodes par compteur Coulter, les mesures par vitesse de sédimentation (reliée à la taille via la loi de Stokes) et la microscopie. Ces techniques permettent de mesurer un diamètre de particules et pour certaines d'entre elles une distribution granulométrique. De préférence, les tailles et les distributions de tailles des particules des compositions selon l'invention, sont mesurées par diffusion statique de la lumière au moyen d'un granulometre commercial de type MasterSizer 2000 de chez Malvern. Les données sont traitées sur la base de la théorie de diffusion de Mie. Cette théorie, exacte pour des particules isotropes, permet de déterminer dans le cas de particules non sphériques, un diamètre « effectif » de particules. Cette théorie est notamment décrite dans l'ouvrage de Van de Hulst, H.C., "Light Scattering by Smail Particles," Chapitres 9 et 10, Wiley, New York, 1957.Particle sizes can be measured by different techniques: we can cite in particular light scattering techniques (dynamic and static), Coulter counter methods, measurements by sedimentation speed (related to size via the law of Stokes) and microscopy. These techniques make it possible to measure a particle diameter and for some of them a particle size distribution. Preferably, the sizes and size distributions of the particles of the compositions according to the invention are measured by static light scattering using a commercial granulometer of the MasterSizer 2000 type from Malvern. The data is processed on the basis of Mie diffusion theory. This theory, exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an "effective" diameter of particles. This theory is notably described in the work of Van de Hulst, H.C., "Light Scattering by Smail Particles," Chapters 9 and 10, Wiley, New York, 1957.
La composition est caractérisée par son diamètre « effectif » moyen en volume D[4,3], défini de la manière suivante : ∑V d,The composition is characterized by its mean “effective” diameter in volume D [4.3], defined as follows: ∑V d,
D[4,3] = -D [4.3] = -
∑ i V * ∑ i V *
où Vj représente le volume des particules de diamètre effectif dj. Ce paramètre est notamment décrit dans la documentation technique du granulometre. Les mesures sont réalisées à 25 °C, sur une dispersion de particules diluée, obtenue à partir de la composition de la manière suivante : 1) dilution d'un facteur 100 avec de l'eau, 2) homogénéisation de la solution, 3) repos de la solution durant 18 heures, 4) récupération du surnageant homogène blanchâtre.where Vj represents the volume of particles of effective diameter dj. This parameter is described in particular in the technical documentation of the granulometer. The measurements are carried out at 25 ° C., on a dispersion of dilute particles, obtained from the composition as follows: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) rest of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant.
Le diamètre « effectif » est obtenu en prenant un indice de réfraction de 1 ,33 pour l'eau et un indice de réfraction moyen de 1 ,42 pour les particules.The "effective" diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.42 for particles.
Exemple 1Example 1
Cet exemple illustre la préparation d'une dispersion de particules d'un polymère dans l'isododécane, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle et le macromonomère correspondant à un copolymère polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253).This example illustrates the preparation of a dispersion of particles of a polymer in isododecane, said polymer being obtained by polymerization of methyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group (Kraton L-1253 ).
Dans un réacteur, on charge 2 kg d'heptane, 2 kg d'isododécane, 2,8 kg d'acrylate de méthyle et 1 ,2 kgg de macromonomère du type copolymère de polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253) et 320 g de tertio butyl peroxy-2- éthylhexanoate (Trigonox 21 S).2 kg of heptane, 2 kg of isododecane, 2.8 kg of methyl acrylate and 1.2 kg of macromonomer of the polyethylene / polybutylene copolymer type with methacrylate end group (Kraton L-1253) are loaded into a reactor. ) and 320 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S).
On agite et on chauffe le mélange reactionnel à température ambiante à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu reactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 16 kg d'acrylate de méthyle et 200 g deStir and heat the reaction mixture at room temperature to 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. We maintain the heating with stirring for an additional 15 minutes, then a mixture consisting of 16 kg of methyl acrylate and 200 g of
Trigonox 21S.Trigonox 21S.
On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu reactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans l'isododécaneThe heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isododecane, is obtained.
Le polymère greffé comprend 6% en poids de macromonomère par rapport au poids du polymère.The grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are as follows:
- Masse moléculaire poids Mw = 119900- Molecular mass weight Mw = 119,900
- Masse moléculaire nombre Mn = 16300- Molecular mass number Mn = 16300
- Indice de polydispersité (Mw/Mn) = 7.37- Polydispersity index (Mw / Mn) = 7.37
- Transition vitreuse : 10°C par DSC Mettler ;- Glass transition: 10 ° C by DSC Mettler;
- Extrait sec : 52.4 % dans l'isododécane, réalisé par thermobalance ;- Dry extract: 52.4% in isododecane, produced by thermobalance;
- Granulométrie : 46 nm avec polydispersité de 0,05 réalisée sur Malvern Autosizer Lo-C à 25°C- Granulometry: 46 nm with polydispersity of 0.05 carried out on Malvern Autosizer Lo-C at 25 ° C
La stabilité de la dispersion obtenue est mise en évidence par la mise en œuvre du protocole de stabilité suivant : dans un tube à hémolyse, on place 8 ml de la dispersion réalisée et on centrifuge à 4000 tours/min pendant 15 minutes à l'aide d'une centrifugeuse Jouan C100-S5. Au bout de 15 minutes, on constate qu'il n'y a pas de déphasage ce qui démontre que la dispersion est stable. Exemple 2The stability of the dispersion obtained is demonstrated by the implementation of the following stability protocol: in a hemolysis tube, 8 ml of the dispersion produced are placed and centrifuged at 4000 rpm for 15 minutes using a Jouan C100-S5 centrifuge. After 15 minutes, we see that there is no phase shift, which shows that the dispersion is stable. Example 2
Cet exemple illustre la préparation d'un polymère formant une dispersion de particules dans un solvant carboné, ledit polymère étant obtenu par polymérisation d'acrylate de méthyle, d'acide acrylique et le macromonomère correspondant à un copolymère polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253).This example illustrates the preparation of a polymer forming a dispersion of particles in a carbonaceous solvent, said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the macromonomer corresponding to a polyethylene / polybutylene copolymer with methacrylate end group ( Kraton L-1253).
Dans un réacteur de 1 litre, on charge 200 g d'heptane, 200 g d'isododécane, 28 g d'acrylate de méthyle et 12 g de macromonomère du type copolymère de polyéthylène/polybutylène à groupement terminal méthacrylate (Kraton L-1253) et 3.2 g de tertio butyl peroxy-2-éthylhexanoate (Trigonox 21 S).200 g of heptane, 200 g of isododecane, 28 g of methyl acrylate and 12 g of macromonomer of the polyethylene / polybutylene copolymer type with methacrylate end group (Kraton L-1253) are loaded into a 1 liter reactor. and 3.2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S).
On agite et on chauffe le mélange reactionnel à température ambiante à 90°C en 1 heure. Après 15 minutes à 90°C, on observe un changement d'aspect du milieu reactionnel, qui passe d'un aspect transparent à un aspect laiteux. On maintient le chauffage sous agitation pendant 15 minutes supplémentaires puis on ajoute goutte à goutte pendant 1 heure un mélange constitué par 150 g d'acrylate de méthyle, 10g d'acide acrylique et 2 g de Trigonox 21 S. On laisse ensuite le chauffage pendant 4 heures à 90°C puis on distille l'heptane du milieu reactionnel. A l'issue de cette opération de distillation, on obtient une dispersion de particules de polymère ainsi préparé stable dans l'isododécaneStir and heat the reaction mixture at room temperature to 90 ° C in 1 hour. After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. The heating is kept under stirring for an additional 15 minutes, then a mixture consisting of 150 g of methyl acrylate, 10 g of acrylic acid and 2 g of Trigonox 21 S is added dropwise for 1 hour. 4 hours at 90 ° C. then the heptane is distilled from the reaction medium. At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isododecane, is obtained.
Le polymère greffé comprend 6 % en poids de macromonomère par rapport au poids du polymère.The grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
Les caractéristiques du polymère et des particules formées par ledit polymère sont les suivantes :The characteristics of the polymer and of the particles formed by said polymer are: following:
- Masse moléculaire poids Mw=143639- molecular weight Mw = 143639
- Masse moléculaire nombre Mn=23965- Molecular mass number Mn = 23965
- Indice de polydispersité (Mw/Mn)= 5.99- Polydispersity index (Mw / Mn) = 5.99
- Extrait sec théorique : 51.3 % dans l'isododécane- Theoretical dry extract: 51.3% in isododecane
- Granulométrie : 48 nm avec polydispersité de 0,04 réalisée sur Malvern Autosizer Lo-C à 25°C ;- Grain size: 48 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 ° C;
Après la mise en œuvre du protocole de stabilité conformément à l'exemple 1 , on constate que la dispersion obtenue est stable.After the implementation of the stability protocol in accordance with Example 1, it is found that the dispersion obtained is stable.
Exemple 3 : Stick de rouge à lèyresExample 3: Stick of lipstick
Figure imgf000060_0001
Figure imgf000060_0001
Dans un poêlon, on introduit la cire, la phase huileuse et les pigments sous laIn a pan, the wax, the oily phase and the pigments are introduced under the
forme d'un broyât dans la phase huileuse contenant la PVP eicosene. Le mélange est mis à fondre à 100°C sous agitation Rayneri. Lorsque la préparation est liquide, on laisse l'ensemble à 100°C pendant 40 minutes. On introduit alors les ingrédients volatils ou contenant des solvants volatils. Le poêlon est couvert pour limiter les évaporations et le mélange est laissé sous agitation pendant 1 O minutes. La formule est alors coulée à 42°C avant d'être placée au congélateur. On démoule lorsque la température du moule est d'environ 4°C.form of a ground material in the oily phase containing the PVP eicosene. The mixture is melted at 100 ° C with Rayneri stirring. When the preparation is liquid, the whole is left at 100 ° C. for 40 minutes. The volatile ingredients or those containing volatile solvents are then introduced. The pan is covered to limit evaporation and the mixture is left stirring for 10 minutes. The formula is then poured at 42 ° C before being placed in the freezer. It is removed from the mold when the temperature of the mold is approximately 4 ° C.
Le transfert de cette formule a été mesuré selon le protocole décritThe transfer of this formula was measured according to the protocol described
précédemment. Il est égal à 1 ,85 ± 0,1.previously. It is equal to 1.85 ± 0.1.
Exemple 4 : Stick de rouge à lèvresExample 4: Lipstick Stick
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000061_0001
Figure imgf000062_0001
Mode opératoireProcedure
Dans un poêlon, sous agitation Rayneri, on introduit les cires, les pâtes pigmentaires et l'ester de saccharose, on se place à 105°C, on laisse tourner 3O minutes, puis on ajoute les nacres, on ajoute ensuite la dispersion de polymère et le parfum, on laisse tourner 10 minutes, puis on coule dans un moule à 42°C. On place le moule au congélateur et on démoule lorsque le moule est à environ 4°C. Le transfert mesuré selon le protocole décrit précédemment est égal à 1,2.In a pan, with Rayneri stirring, the waxes, the pigment pastes and the sucrose ester are introduced, the mixture is placed at 105 ° C., the mixture is left to turn for 30 minutes, then the nacres are added, then the polymer dispersion is added. and the perfume, it is left to rotate for 10 minutes, then it is poured into a mold at 42 ° C. Place the mold in the freezer and unmold when the mold is at around 4 ° C. The transfer measured according to the protocol described above is equal to 1.2.
Exemple 5 : Stick de rouge à lèyresExample 5: Stick of lipstick
Figure imgf000062_0002
Cette composition a été préparée selon le même mode opératoire que celui de
Figure imgf000062_0002
This composition was prepared according to the same procedure as that of
l'exemple 1.Example 1.
Exemple 6 : MascaraExample 6: Mascara
Figure imgf000063_0001
Figure imgf000063_0001
Mode opératoire : Cette composition peut être préparée de manière standard par formation à chaud d'une émulsion cire dans eau.Procedure: This composition can be prepared in a standard manner by hot formation of a wax in water emulsion.
On chauffe la phase grasse (phase A) contenant la cire et l'acide stéarique jusqu'à fusion complète de l'ensemble des constituants. Ensuite, la dispersion de polymère de l'exemple 2 et les pigments sont incorporés sous agitation à la phase huileuse. Parallèlement, la phase aqueuse (phase B) contenant le neutralisant (Triéthanolamine), les polymères gélifiants sont portés à une température au moins égale à la température de la phase grasse. La phase aqueuse est ensuite additionnée sur la phase huileuse, sous forte agitation (3000rpm), pour former l'émulsion à chaud. L'agitation, la température sont maintenues durant environ 30 minutes.The fatty phase is heated (phase A) containing the wax and the stearic acid until all the constituents have completely melted. Then, the polymer dispersion of Example 2 and the pigments are incorporated with stirring in the oily phase. In parallel, the aqueous phase (phase B) containing the neutralizer (Triethanolamine), the gelling polymers are brought to a temperature at least equal to the temperature of the phase fat. The aqueous phase is then added to the oily phase, with vigorous stirring (3000rpm), to form the hot emulsion. Agitation and temperature are maintained for approximately 30 minutes.
Une agitation modérée à la pâle est ensuite appliquée jusqu'à retour à la température ambiante. Moderate stirring in the pale is then applied until return to room temperature.

Claims

REVENDICATIONS
1. Composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, une dispersion de particules d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide.1. Cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase.
2. Composition selon la revendication précédente, caractérisée par le fait que le polymère greffé non siliconé contient majoritairement un macromonomère carboné et contient éventuellement au plus 7 % en poids de macromonomère siliconé.2. Composition according to the preceding claim, characterized in that the non-silicone grafted polymer mainly contains a carbon macromonomer and optionally contains at most 7% by weight of silicone macromonomer.
3. Composition selon la revendication 1 ou 2, caractérisée par le fait que le polymère greffé non siliconé est exempt de macromonomère siliconé.3. Composition according to claim 1 or 2, characterized in that the non-silicone grafted polymer is free of silicone macromonomer.
4. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique greffé non siliconé comprend un squelette éthylenique insoluble dans ladite phase grasse liquide et des chaînes latérales liées de manière covalente audit squelette et solubles dans ladite phase grasse liquide.4. Composition according to one of the preceding claims, characterized in that the non-silicone grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase and side chains covalently linked to said skeleton and soluble in said liquid fatty phase.
5. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique greffé est un polymère acrylique greffé.5. Composition according to one of the preceding claims, characterized in that the grafted ethylenic polymer is a grafted acrylic polymer.
6. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique est dispersé en l'absence de stabilisant additionnel en surface des particules. 6. Composition according to one of the preceding claims, characterized in that the ethylenic polymer is dispersed in the absence of additional stabilizer at the surface of the particles.
7. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique greffé en dispersion est un polymère acrylique susceptible d'être obtenu par polymérisation radicalaire dans un milieu organique de polymérisation :7. Composition according to one of the preceding claims, characterized in that the ethylenic polymer grafted in dispersion is an acrylic polymer capable of being obtained by radical polymerization in an organic polymerization medium:
- d'au moins un monomère acrylique, et éventuellement d'au moins un monomère additionnel vinylique non acrylique, pour former ledit squelette insoluble ; et- At least one acrylic monomer, and optionally at least one additional non-acrylic vinyl monomer, to form said insoluble skeleton; and
- d'au moins un macromonomère carboné comportant un groupe terminal polymérisable pour former les chaînes latérales, ledit macromonomère ayant une masse moléculaire moyenne en poids supérieure ou égale à 200 et la teneur en macromonomère polymérisé représentant de 0,05 à 20% en poids du polymère.- At least one carbon macromonomer comprising a polymerizable end group to form the side chains, said macromonomer having a weight average molecular mass greater than or equal to 200 and the content of polymerized macromonomer representing from 0.05 to 20% by weight of the polymer.
8. Composition selon la revendication précédente, caractérisée en ce que le monomère, acrylique est choisi parmi, seul ou en mélange, les monomères suivants, ainsi que leurs sels :8. Composition according to the preceding claim, characterized in that the acrylic monomer is chosen from, alone or as a mixture, the following monomers, as well as their salts:
-(i) les (méth)acrylates de formule :- (i) (meth) acrylates of formula:
CH2=C COOR2 CH 2 = C COOR 2
Ri dans laquelle :Ri in which:
- R-i désigne un atome d'hydrogène ou un groupe méthyle ; - R2 représente un groupe choisi parmi :- Ri denotes a hydrogen atom or a methyl group; - R 2 represents a group chosen from:
- un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S; et/ou pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C-1-C4; et/ou pouvant être substitué par au moins un groupe polyoxyalkylène, notamment polyoxyéthylène et/ou polyoxypropylène, ledit groupe polyoxyalkylène étant constitué par la répétition de 5 à 30 motifs oxyalkylène ;- a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls in C-1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units;
- un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S, et/ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I) ;a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and / or possibly comprising one or more substituents chosen from OH and the atoms of halogen (F, Cl, Br, I);
-(ii) les (méth)acrylamides de formule :- (ii) the (meth) acrylamides of formula:
Figure imgf000067_0001
dans laquelle :
Figure imgf000067_0001
in which :
- R3 désigne un atome d'hydrogène ou un groupe méthyle ;- R 3 denotes a hydrogen atom or a methyl group;
- R et R5, identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle, linéaire ou ramifié, comportant de 1 à 6 atomes de carbone, pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C-j-C4;ou- R and R 5 , identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched Cj-C4 alkyls; or
- R4 représente un atome d'hydrogène et R5 représente un groupe 1 ,1-diméthyl-3- oxobutyle ;- R 4 represents a hydrogen atom and R 5 represents a group 1, 1-dimethyl-3-oxobutyl;
-(iii) les monomères (méth)acryliques comprenant au moins une fonction acide carboxylique, phosphorique ou sulfonique, tels que l'acide acrylique, l'acide méthacrylique, l'acide acrylamidopropanesulfonique.- (iii) (meth) acrylic monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid.
9. Composition selon la revendication 7 ou 8, caractérisée en ce que le monomère acrylique est choisi parmi les (méth)acrylates de méthyle, d'éthyle, de propyle, de butyle, d'isobutyle; les (méth)acrylates de methoxyéthyle ou d'éthoxyethyle ; le méthacrylate de trifluoroéthyle; le méthacrylate de diméthylaminoéthyle, le méthacrylate de diéthylaminoéthyle, le (méth)acrylate de 2-hydroxypropyle, le (méth)acrylate de 2- hydroxyéthyle ; le diméthylaminopropylméthacrylamide; et leurs sels.9. Composition according to claim 7 or 8, characterized in that the acrylic monomer is chosen from methyl, ethyl, propyl, butyl (meth) acrylates, isobutyl; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; dimethylaminopropylmethacrylamide; and their salts.
10. Composition selon l'une des revendications 7 à 9, caractérisée en ce que le monomère acrylique est choisi parmi l'acrylate de méthyle, l'acrylate de methoxyéthyle, le méthacrylate de méthyle, le méthacrylate de 2-hydroxyéthyle, l'acide (meth)acrylique, le méthacrylate de diméthylaminoéthyle, et leurs mélanges.10. Composition according to one of claims 7 to 9, characterized in that the acrylic monomer is chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acid (meth) acrylic, dimethylaminoethyl methacrylate, and mixtures thereof.
11. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère acrylique greffé ne contient pas de monomère vinylique non acrylique additionnel.11. Composition according to one of the preceding claims, characterized in that the grafted acrylic polymer does not contain any additional non-acrylic vinyl monomer.
12. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que le polymère greffé non siliconé comprend de l'acide (méth)acrylique.12. Composition according to any one of the preceding claims, characterized in that the non-silicone grafted polymer comprises (meth) acrylic acid.
13. Composition selon l'une quelconque des revendications 7 à 12, caractérisée par le fait que les monomères acryliques comprennent au moins l'acide (méth)acrylique et au moins un monomère choisi parmi :13. Composition according to any one of claims 7 to 12, characterized in that the acrylic monomers comprise at least (meth) acrylic acid and at least one monomer chosen from:
-(i) les (méth)acrylates de formule :- (i) (meth) acrylates of formula:
Figure imgf000068_0001
dans laquelle :
Figure imgf000068_0001
in which :
- Ri désigne un atome d'hydrogène ou un groupe méthyle ; - R2 représente un groupe choisi parmi :- Ri denotes a hydrogen atom or a methyl group; - R 2 represents a group chosen from:
- un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S; et/ou pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en C1 -C4; et/ou pouvant être substitué par au moins un groupe polyoxyalkylène, notamment polyoxyéthylène et/ou polyoxypropylène, ledit groupe polyoxyalkylène étant constitué par la répétition de 5 à 30 motifs oxyalkylène ; - un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, ledit groupe pouvant comporter dans sa chaîne un ou plusieurs hétéroatomes choisis parmi O, N et S, et/ou pouvant comporter un ou plusieurs substituants choisis parmi OH et les atomes d'halogène (F, Cl, Br, I) ;- a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S; and / or possibly comprising one or more substituents chosen from -OH, the halogen atoms (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched alkyls C1-C4; and / or may be substituted by at least one polyoxyalkylene group, in particular polyoxyethylene and / or polyoxypropylene, said polyoxyalkylene group consisting of the repetition of 5 to 30 oxyalkylene units; a cyclic alkyl group comprising from 3 to 6 carbon atoms, said group possibly comprising in its chain one or more heteroatoms chosen from O, N and S, and / or possibly comprising one or more substituents chosen from OH and the atoms of halogen (F, Cl, Br, I);
-(ii) les (méth)acrylamides de formule :- (ii) the (meth) acrylamides of formula:
Figure imgf000069_0001
dans laquelle :
Figure imgf000069_0001
in which :
- R3 désigne un atome d'hydrogène ou un groupe méthyle ;- R 3 denotes a hydrogen atom or a methyl group;
- R4 et R5, identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle, linéaire ou ramifié, comportant de 1 à 6 atomes de carbone, pouvant comporter un ou plusieurs substituants choisis parmi -OH, les atomes d'halogène (F, Cl, Br, I) et -NR'R" avec R' et R" identiques ou différents choisis parmi les alkyles linéaires ou ramifiés en Cι-C4;ou- R 4 and R 5 , identical or different, represent a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, which can comprise one or more substituents chosen from -OH, the atoms of halogen (F, Cl, Br, I) and -NR'R "with R 'and R" identical or different chosen from linear or branched Cι-C4 alkyls; or
- R4 représente un atome d'hydrogène et R5 représente un groupe 1 ,1-diméthyl-3- oxobutyle ; - R 4 represents a hydrogen atom and R 5 represents a group 1, 1-dimethyl-3-oxobutyl;
14. Composition selon l'une quelconque des revendications 7 à 13, caractérisée par le fait que les monomères acryliques comprennent au moins l'acide (méth)acrylique et au moins un monomère choisi parmi les (méth)acrylates d'alkyle en C-1-C3.14. Composition according to any one of claims 7 to 13, characterized in that the acrylic monomers comprise at least (meth) acrylic acid and at least one monomer chosen from C- alkyl (meth) acrylates 1-C3.
15. Composition selon l'une quelconque des revendications 12 à 14, caractérisée par le fait que l'acide (méth)acrylique est présent en une teneur d'au moins 5 % en poids, par rapport au poids total du polymère, notamment allant de 5 % à 80 % en poids, de préférence d'au moins 10 % en poids, notamment allant de 10 % en poids à 70 % en poids, préférentiellement d'au moins 15 % en poids, notamment allant de 15 % à 60 % en poids.15. Composition according to any one of claims 12 to 14, characterized in that the (meth) acrylic acid is present in a content of at least 5% by weight, relative to the total weight of the polymer, in particular ranging from 5% to 80% by weight, preferably at least 10% by weight, especially ranging from 10% by weight to 70% by weight, preferably at least 15% by weight, especially ranging from 15% to 60 % in weight.
16. Composition selon la revendication 7, caractérisée en ce que le polymère acrylique greffé est susceptible d'être obtenu par polymérisation radicalaire d'un ou plusieurs monomère(s) acrylique(s) et d'un un ou plusieurs monomère(s) additionnel(s) vinylique(s) non acrylique(s), et dudit macromonomère carboné.16. Composition according to Claim 7, characterized in that the grafted acrylic polymer is capable of being obtained by radical polymerization of one or more acrylic monomer (s) and of one or more additional monomer (s) (s) non-acrylic vinyl (s), and said carbonaceous macromonomer.
17. Composition selon la revendication précédente, caractérisée en ce que les monomères additionnels vinyliques non acryliques sont choisis parmi : - les esters vinylique de formule : R6-COO-CH=CH2 dans laquelle R6 représente un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes, ou un groupe alkyle cyclique comportant de 3 à 6 atomes de carbone et/ou un groupe aromatique, par exemple de type benzénique, anthracénique, et naphtalénique ;17. Composition according to the preceding claim, characterized in that the additional non-acrylic vinyl monomers are chosen from: - the vinyl esters of formula: R 6 -COO-CH = CH 2 in which R 6 represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or a cyclic alkyl group comprising from 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene, and naphthalene type;
- les monomères vinyliques non acryliques comprenant au moins une fonction acide carboxylique, phosphorique ou sulfonique, tels que l'acide crotonique, l'anhydride maléique, l'acide itaconique, l'acide fumarique, l'acide maléique, l'acide styrènesulfonique, l'acide vinylbenzoïque, l'acide vinylphosphorique et les sels de ceux-ci ;- non-acrylic vinyl monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acid styrenesulfonic, vinylbenzoic acid, vinylphosphoric acid and the salts thereof;
- les monomères vinyliques non acryliques comprenant au moins une fonction aminé tertiaire, tels que la 2-vinylpyridine, la 4-vinylpyridine ;- non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine;
- et leurs mélanges.- and their mixtures.
18. Composition selon la revendication 16 ou 17, caractérisée en ce que les monomères acryliques représentent de 50 à 100 % en poids, de préférence de 60 à 100 % en poids , préférentiellement de 70 à 100 % en poids du mélange monomères acryliques + monomères vinyliques non acryliques éventuels.18. Composition according to claim 16 or 17, characterized in that the acrylic monomers represent from 50 to 100% by weight, preferably from 60 to 100% by weight, preferably from 70 to 100% by weight of the mixture of acrylic monomers + monomers possible non-acrylic vinyls.
19. Composition selon l'une des revendications 7 à 18, caractérisée en ce que le macromonomère carboné comporte à une des extrémités de la chaîne un groupe terminal polymérisable choisi parmi un groupe vinyle ou un groupe (méth)acrylate, et de préférence un groupe (méth)acrylate.19. Composition according to one of claims 7 to 18, characterized in that the carbon macromonomer comprises at one of the ends of the chain a polymerizable end group chosen from a vinyl group or a (meth) acrylate group, and preferably a group (meth) acrylate.
20. Composition selon la revendication 19, caractérisée en ce que le macromonomère carboné est choisi parmi :20. Composition according to claim 19, characterized in that the carbon macromonomer is chosen from:
- (i) les homopolymères et les copolymères d'acrylate ou de méthacrylate d'alkyle en C8-C22 linéaire ou ramifié et ayant un groupe terminal polymérisable choisi parmi les groupes vinyle ou (méth)acrylate ;- (i) homopolymers and copolymers of linear or branched C8-C22 alkyl acrylate or methacrylate and having a polymerizable end group chosen from vinyl or (meth) acrylate groups;
- (ii) les polyoléfines ayant un groupe terminal à insaturation éthylenique polymérisable.- (ii) polyolefins having a terminal group with polymerizable ethylenic unsaturation.
21. Composition selon la revendication 19 ou 20, caractérisée en ce que le macromonomère carboné est choisi parmi : - (i) les macromonomères de poly(acrylate d'éthyl-2 hexyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(acrylate de dodécyle) à extrémité mono(méth)acrylate ; les macromonomères de poly(méthacrylate de dodécyle) ; les macromonomères de poly(acrylate de stéaryle) à extrémité mono(méth)acrylate ; les macromonomères de poly (méthacrylate de stéaryle) à extrémité mono(méth)acrylate ;21. Composition according to claim 19 or 20, characterized in that the carbon macromonomer is chosen from: - (i) macromonomers of poly (2-ethylhexyl acrylate) with a mono (meth) acrylate end; macromonomers of poly (dodecyl acrylate) with a mono (meth) acrylate end; macromonomers of poly (dodecyl methacrylate); poly (stearyl acrylate) macromonomers with mono (meth) acrylate end; poly (stearyl methacrylate) macromonomers with mono (meth) acrylate end;
- (ii) les macromonomères de polyethylene, les macromonomères de polypropylène, les macromonomères de copolymère polyéthylène/polypropylène, les macromonomères de copolymère polyéthylène/polybutylène, les macromonomères de polyisobutylène, les macromonomères de polybutadiène, les macromonomères de polyisoprène, les macromonomères de polybutadiène, les macromonomères de poly(éthylène/butylène)-polyisoprène, ces macromonomères ayant un groupement terminal (méth)acrylate.- (ii) macromonomers of polyethylene, macromonomers of polypropylene, macromonomers of polyethylene / polypropylene copolymer, macromonomers of polyethylene / polybutylene copolymer, macisonomers of polyisobutylene, macromonomers of polybutadiene, macromonomers of polyisoprene, macromonomers of polybutadiene, poly (ethylene / butylene) -polyisoprene macromonomers, these macromonomers having a terminal (meth) acrylate group.
22. Composition selon l'une des revendications 19 à 21 , caractérisée en ce le macromonomère carboné est choisi parmi :22. Composition according to one of claims 19 to 21, characterized in that the carbon macromonomer is chosen from:
- (i) les macromonomères de poly(acrylate d'éthyl-2-hexyle) à extrémité mono(méth)acrylate, les macromonomères de poly(acrylate de dodécyle) à extrémité mono(méth)acrylate ;- (i) macromonomers of poly (ethyl-2-hexyl acrylate) with mono (meth) acrylate end, macromonomers of poly (dodecyl acrylate) with mono (meth) acrylate end;
- (ii) le méthacrylate de poly(éthylène/butylène).- (ii) poly (ethylene / butylene) methacrylate.
23. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère greffé non siliconé est choisi parmi les polymères obtenus par polymérisation23. Composition according to one of the preceding claims, characterized in that the non-silicone grafted polymer is chosen from the polymers obtained by polymerization
- de l'acrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans un solvant choisi parmi l'isododécane, l'isononylisononanoate, l'octyldodécanol , le malate de diisostéaryle, un benzoate d'alkyl C-ι2-C15 ;- methyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in a solvent chosen from isododecane, isononylisononanoate, octyldodecanol, diisostearyl malate, a C-ι 2 -C 15 alkyl benzoate;
- de l'acrylate de methoxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans l'isododécane ;- methoxyethyl acrylate and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de méthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans l'isododécane ;- Methyl acrylate / methyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in isododecane;
- des monomères acrylate de méthyle / acide acrylique et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans l'isododécane ;- Methyl acrylate / acrylic acid monomers and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de diméthylaminoéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans l'isododécane ;- Methyl acrylate / dimethylaminoethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in isododecane;
- des monomères acrylate de méthyle / méthacrylate de 2-hydroxyéthyle et du macromonomère polyéthylène/polybutylène à groupement terminal méthacrylate, en particulier dans l'isododécane.- Methyl acrylate / 2-hydroxyethyl methacrylate monomers and polyethylene / polybutylene macromonomer with methacrylate end group, in particular in isododecane.
24. Composition selon l'une des revendications 7 à 23, caractérisée en ce que le macromonomère a une masse moléculaire moyenne en poids supérieure ou égale à 300, préférentiellement supérieure ou égale à 500, et plus préférentiellement supérieure à 600.24. Composition according to one of claims 7 to 23, characterized in that the macromonomer has a weight-average molecular mass greater than or equal to 300, preferably greater than or equal to 500, and more preferably greater than 600.
25. Composition selon l'une des revendications 7 à 24, caractérisée en ce que le macromonomère a une masse moléculaire moyenne en poids (Mw) allant de 300 à 100 000, de préférence allant de 500 à 50 000, préférentiellement allant de 800 à 20 000, plus préférentiellement allant de 800 à 10000, et encore plus préférentiellement allant de 800 à 6000. 25. Composition according to one of claims 7 to 24, characterized in that the macromonomer has a weight-average molecular mass (Mw) ranging from 300 to 100,000, preferably ranging from 500 to 50,000, preferably ranging from 800 to 20,000, more preferably ranging from 800 to 10,000, and even more preferably ranging from 800 to 6,000.
26. Composition selon l'une des revendications 7 à 25, caractérisée en ce que le macromonomère carboné polymérisé représente de 0,1 à 15 % en poids du poids total du polymère, de préférence de 0,2 à 10 % en poids, et préférentiellement de 0,3 à 8 % en poids.26. Composition according to one of claims 7 to 25, characterized in that the polymerized carbon macromonomer represents from 0.1 to 15% by weight of the total weight of the polymer, preferably from 0.2 to 10% by weight, and preferably from 0.3 to 8% by weight.
27. Composition selon l'une des revendications précédentes, caractérisée en ce que la phase grasse liquide comprend un composé organique liquide choisi parmi :27. Composition according to one of the preceding claims, characterized in that the liquid fatty phase comprises a liquid organic compound chosen from:
- les composés organiques liquides ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2,- liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of 18 (MPa) 1/2 or less,
- les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 ; et- monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2 ; and
- leurs mélanges.- their mixtures.
28. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle comprend une huile volatile.28. Composition according to any one of the preceding claims, characterized in that it comprises a volatile oil.
29. Composition selon la revendication précédente, caractérisée par le fait qu'elle comprend une huile volatile choisie parmi l'isododécane, l'isodécane, l'isohexadécane.29. Composition according to the preceding claim, characterized in that it comprises a volatile oil chosen from isododecane, isodecane, isohexadecane.
30. Composition selon la revendication 28 ou 29, caractérisée par le fait que l'huile volatile est présente en une teneur allant de 1 % à 70 % en poids, par rapport au poids total de la composition, de préférence allant de 5 % à 50 % en poids, et préférentiellement allant de 10 % à 35 % en poids.30. Composition according to Claim 28 or 29, characterized in that the volatile oil is present in a content ranging from 1% to 70% by weight, relative to the total weight of the composition, preferably ranging from 5% to 50% by weight, and preferably ranging from 10% to 35% by weight.
31. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle comprend une huile non volatile. 31. Composition according to any one of the preceding claims, characterized in that it comprises a non-volatile oil.
32. Composition selon la revendication 31 , caractérisée par le fait que l'huile non volatile est présente en une teneur allant de 1 % à 80 % en poids, par rapport au poids total de la composition, de préférence allant de 5 % à 60 % en poids, et préférentiellement allant de 10 % à 50 % en poids.32. Composition according to Claim 31, characterized in that the non-volatile oil is present in a content ranging from 1% to 80% by weight, relative to the total weight of the composition, preferably ranging from 5% to 60 % by weight, and preferably ranging from 10% to 50% by weight.
33. Composition selon l'une des revendications précédentes, caractérisée en ce que la phase grasse liquide est une phase grasse liquide non siliconée.33. Composition according to one of the preceding claims, characterized in that the liquid fatty phase is a non-silicone liquid fatty phase.
34. Composition selon la revendication 33, caractérisée en ce que la phase grasse liquide non siliconée est constituée d'au moins 50% en poids d'au moins un composé liquide organique non siliconé choisi parmi :34. Composition according to claim 33, characterized in that the non-silicone liquid fatty phase consists of at least 50% by weight of at least one non-silicone organic liquid compound chosen from:
- les composés liquides organiques non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1 2 ;- non-silicone organic liquid compounds having an overall solubility parameter according to the Hansen solubility space less than or equal to 18 (MPa) 1 2 ;
- les monoalcools liquides ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 ; et- liquid monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2 ; and
- leurs mélanges.- their mixtures.
35. Composition selon la revendication 34, caractérisée en ce que le composé organique liquide non siliconé est choisi parmi les composés organiques liquides non siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur à 18 (MPa)1 2 ; les monoalcools liquides ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1 2 ; et leurs mélanges.35. Composition according to claim 34, characterized in that the non-silicone liquid organic compound is chosen from non-silicone liquid organic compounds having an overall solubility parameter according to the Hansen solubility space of less than 18 (MPa) 1 2 ; liquid monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1 2 ; and their mixtures.
36. Composition selon la revendication 35, caractérisée en ce que le composé liquide organique non siliconé ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2 est choisi parmi les huiles carbonées, hydrocarbonées, fluorées, seules ou en mélange ; les alcanes linéaires, ramifiés et/ou cycliques, éventuellement volatils; les esters et notamment les esters linéaires, ramifiés ou cycliques, ayant au moins 6 atomes de carbone; les cétones et notamment les cétones ayant au moins 6 atomes de carbone; les éthers et notamment les éthers ayant au moins 6 atomes de carbone.36. Composition according to claim 35, characterized in that the non-silicone organic liquid compound having an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1/2 is chosen from carbon oils, hydrocarbon, fluorinated, alone or in mixture; linear, branched and / or cyclic alkanes, optionally volatile; esters and in particular linear, branched or cyclic esters, having at least 6 carbon atoms; ketones and in particular ketones having at least 6 carbon atoms; ethers and in particular ethers having at least 6 carbon atoms.
37. Composition selon la revendication 35, caractérisée en ce que les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 20 (MPa)1/2 sont choisis parmi les monoalcools gras aliphatiques ayant 6 à 30 atomes de carbone, la chaîne hydrocarbonée ne comportant pas de groupement de substitution, et notamment l'alcool oléique, le décanol, et l'alcool linoléique.37. Composition according to claim 35, characterized in that the monoalcohols having an overall solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 are chosen from aliphatic fatty monoalcohols having 6 to 30 carbon atoms, the hydrocarbon chain containing no substitution group, and in particular oleic alcohol, decanol, and linoleic alcohol.
38. Composition selon l'une des revendications 33 à 37, caractérisée en ce que la phase grasse liquide non siliconée comprend moins de 50 % en poids de composés organiques liquides siliconés ayant un paramètre de solubilité global selon l'espace de solubilité de Hansen inférieur ou égal à 18 (MPa)1/2.38. Composition according to one of claims 33 to 37, characterized in that the non-silicone liquid fatty phase comprises less than 50% by weight of silicone liquid organic compounds having an overall solubility parameter according to the lower Hansen solubility space or equal to 18 (MPa) 1/2 .
39. Composition selon la revendication 38, caractérisée en ce que le composé liquide organique siliconé comprend une huile siliconée volatile.39. Composition according to claim 38, characterized in that the organic silicone liquid compound comprises a volatile silicone oil.
40. Composition selon la revendication 39, caractérisée en ce que l'huile siliconée volatile est choisie parmi l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasiloxane, le dodécaméthylcyclohexasiloxane, l'heptaméthylhexyltrisiloxane, l'heptaméthyloctyltrisiloxane, l'octaméthyltrisiloxane, le décaméthyltétrasiloxane, et leurs mélanges. 40. Composition according to claim 39, characterized in that the volatile silicone oil is chosen from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, etamethyltrisiloxane.
41. Composition selon la revendication 38, caractérisée en ce que le composé liquide organique siliconé comprend une huile siliconée non volatile.41. Composition according to claim 38, characterized in that the organic silicone liquid compound comprises a non-volatile silicone oil.
42. Composition selon la revendication 41 , caractérisée en ce que l'huile siliconée non volatile est choisie parmi les polydialkylsiloxanes non volatils; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone; les siliconés phénylées ; les polysiloxanes modifiés par des acides gras (notamment en C8-C20). des alcools gras (notamment en Cg-C2θ) ou des polyoxyalkylènes (notamment polyoxyéthylène et/ou polyoxypropylène); les polysiloxanes aminées ; les polysiloxanes à groupement hydroxyles; les polysiloxanes fluorés comportant un groupement fluoré pendant ou en bout de chaîne siliconée ayant de 1 à 12 atomes de carbone dont tout ou partie des hydrogène sont substitués par des atomes de fluor ; et leurs mélanges.42. Composition according to claim 41, characterized in that the non-volatile silicone oil is chosen from non-volatile polydialkylsiloxanes; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones; polysiloxanes modified with fatty acids (especially C8-C20). fatty alcohols (especially Cg-C2θ) or polyoxyalkylenes (especially polyoxyethylene and / or polyoxypropylene); amino polysiloxanes; polysiloxanes containing hydroxyl groups; fluorinated polysiloxanes comprising a fluorinated group during or at the end of the silicone chain having from 1 to 12 carbon atoms of which all or part of the hydrogen are substituted by fluorine atoms; and their mixtures.
43. Composition selon l'une des revendications 33 à 37, caractérisée en ce que la phase grasse liquide non siliconée ne contient pas de composés organiques liquides siliconés.43. Composition according to one of claims 33 to 37, characterized in that the non-silicone liquid fatty phase does not contain liquid silicone organic compounds.
44. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère greffé a une masse moléculaire moyenne en poids (Mw) comprise entre 1044. Composition according to one of the preceding claims, characterized in that the grafted polymer has a weight-average molecular mass (Mw) of between 10
000 et 300 000, notamment entre 20 000 et 200 000, mieux encore entre 25 000 et 150 000.000 and 300,000, especially between 20,000 and 200,000, better still between 25,000 and 150,000.
45. Composition selon l'une des revendications précédentes, caractérisée en ce que particules de polymère éthylenique greffé ont une taille moyenne allant de 10 à 400 nrn, de préférence allant de 20 à 200 nm. 45. Composition according to one of the preceding claims, characterized in that the grafted ethylenic polymer particles have an average size ranging from 10 to 400 nm, preferably ranging from 20 to 200 nm.
46. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique greffé est un polymère filmogène.46. Composition according to one of the preceding claims, characterized in that the grafted ethylenic polymer is a film-forming polymer.
47. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère éthylenique greffé est présent en une teneur en matière sèche allant de 1 à 70% en poids par rapport au poids total de la composition, mieux de 5 à 60% en poids, de préférence allant de 6 à 45% et mieux allant de 8 à 40% en poids.47. Composition according to one of the preceding claims, characterized in that the grafted ethylenic polymer is present in a dry matter content ranging from 1 to 70% by weight relative to the total weight of the composition, better still from 5 to 60% by weight, preferably ranging from 6 to 45% and better still ranging from 8 to 40% by weight.
48. Composition selon l'une des revendications précédentes, caractérisée par le fait que le polymère greffé est tel que lorsqu'il est dispersé en une quantité suffisante dans la composition, cette dernière est apte à former un dépôt ayant un transfert inférieur ou égal à 35 %.48. Composition according to one of the preceding claims, characterized in that the grafted polymer is such that when it is dispersed in a sufficient amount in the composition, the latter is capable of forming a deposit having a transfer less than or equal to 35%.
49. Composition selon l'une des revendications précédentes, caractérisée par le fait que le polymère greffé est tel que lorsqu'il est dispersé en une quantité suffisante dans la composition, cette dernière est apte à former un dépôt ayant un transfert inférieur ou égal à 30 %, de préférence inférieur ou égal à 25 %, de préférence inférieur ou égal à 20 %, de préférence inférieur ou égal à 15 %, de préférence inférieur ou égal à 10 %, de préférence inférieur ou égal à 5 %.49. Composition according to one of the preceding claims, characterized in that the grafted polymer is such that when it is dispersed in a sufficient amount in the composition, the latter is capable of forming a deposit having a transfer less than or equal to 30%, preferably less than or equal to 25%, preferably less than or equal to 20%, preferably less than or equal to 15%, preferably less than or equal to 10%, preferably less than or equal to 5%.
50. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle comprend au moins un corps gras solides à température ambiante choisi parmi les cires, les corps gras pâteux, les gommes et leurs mélanges.50. Composition according to any one of the preceding claims, characterized in that it comprises at least one fatty substance solid at room temperature chosen from waxes, pasty fatty substances, gums and their mixtures.
51. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient de 0,1 à 50 % en poids de cires, par rapport au poids total de la composition, et de préférence de 1 à 30 % en poids. 51. Composition according to any one of the preceding claims, characterized in that it contains from 0.1 to 50% by weight of waxes, relative to the total weight of the composition, and preferably from 1 to 30% by weight. weight.
52. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle comprend une matière colorante.52. Composition according to any one of the preceding claims, characterized in that it comprises a coloring material.
53. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle comprend un ingrédient cosmétique choisi parmi les polymères filmogènes additionnels les vitamines, les épaississants, les gélifiants, les oligo-éléments, les adoucissants, les séquestrants, les parfums, les agents alcalinisants ou acidifiants, les conservateurs, les filtres solaires, les tensioactifs, les anti-oxydants, les fibres, les agents anti-chutes des cheveux, les agents de soin du cil, les agents anti-pelliculaires, les agents propulseurs, ou leurs mélanges.53. Composition according to any one of the preceding claims, characterized in that it comprises a cosmetic ingredient chosen from additional film-forming polymers vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, fibers, anti-hair loss agents, eyelash care agents, anti-dandruff agents, propellants , or their mixtures.
54. Composition cosmétique selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle se présente sous forme de pâte ou de stick.54. Cosmetic composition according to any one of the preceding claims, characterized in that it is in the form of a paste or stick.
55. Composition cosmétique selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle est un rouge à lèvres.55. Cosmetic composition according to any one of the preceding claims, characterized in that it is a lipstick.
56. Composition cosmétique selon l'une quelconque des revendications 1 à 53, caractérisée par le fait qu'elle est un mascara.56. Cosmetic composition according to any one of claims 1 to 53, characterized in that it is a mascara.
57. Composition cosmétique selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle se présente sous forme anhydre.57. Cosmetic composition according to any one of the preceding claims, characterized in that it is in anhydrous form.
58. Composition cosmétique selon l'une quelconque des revendications 1 à 56, caractérisée par le fait qu'elle comprend une phase aqueuse. 58. Cosmetic composition according to any one of claims 1 to 56, characterized in that it comprises an aqueous phase.
59. Composition cosmétique selon la revendication 58, caractérisée par le fait que la phase aqueuse est présente en une teneur allant de 0,1 % à 95 % en poids, par rapport au poids total de la composition, de préférence allant de 1 % à 80 % en poids.59. Cosmetic composition according to claim 58, characterized in that the aqueous phase is present in a content ranging from 0.1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 1% to 80% by weight.
60. Composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, une dispersion de particules d'un polymère éthylenique greffé non siliconé dans une phase grasse liquide et une matière colorante pulvérulente, notamment sous forme de pigments.60. Cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase and a pulverulent coloring matter, in particular in the form of pigments.
61. Composition selon la revendication précédente, caractérisée par le fait que polymère éthylenique greffé non siliconé est conforme à l'une des revendications 2 à 47.61. Composition according to the preceding claim, characterized in that the grafted non-silicone ethylenic polymer conforms to one of claims 2 to 47.
62. Ensemble cosmétique comprenant : a) un récipient délimitant au moins un compartiment, ledit récipient étant fermé par un élément de fermeture ; et b) une composition disposée à l'intérieur dudit compartiment, la composition étant conforme à l'une quelconque des revendications qui précèdent.62. Cosmetic assembly comprising: a) a container delimiting at least one compartment, said container being closed by a closing element; and b) a composition placed inside said compartment, the composition being according to any one of the preceding claims.
63. Ensemble cosmétique selon la revendication 62, caractérisé par le fait que le récipient est formé, au moins pour partie, en au moins un matériau thermoplastique.63. Cosmetic assembly according to claim 62, characterized in that the container is formed, at least in part, of at least one thermoplastic material.
64. Ensemble cosmétique selon la revendication 62, caractérisé par le fait que le récipient est formé, au moins pour partie, en au moins un matériau non thermoplastique, notamment en verre ou en métal.64. Cosmetic assembly according to claim 62, characterized in that the container is formed, at least in part, of at least one non-thermoplastic material, in particular glass or metal.
65. Ensemble selon l'une quelconque des revendications 62 à 64, caractérisé par le fait que, en position fermée du récipient, l'élément de fermeture est vissé sur le récipient. 65. An assembly according to any one of claims 62 to 64, characterized in that, in the closed position of the container, the closing element is screwed onto the container.
66. Ensemble selon l'une quelconque des revendications 62 à 64, caractérisé par le fait que, en position fermée du récipient, l'élément de fermeture est couplé au récipient autrement que par vissage, notamment par encliquetage, collage, ou soudage.66. An assembly according to any one of claims 62 to 64, characterized in that, in the closed position of the container, the closing element is coupled to the container other than by screwing, in particular by snap-fastening, gluing, or welding.
67. Ensemble selon l'une quelconque des revendications 62 à 66, caractérisé par le fait que la composition est pressurisée à l'intérieur du récipient.67. Assembly according to any one of claims 62 to 66, characterized in that the composition is pressurized inside the container.
68. Ensemble selon l'une quelconque des revendications 62 à 66 caractérisé en ce que la composition est sensiblement à la pression atmosphérique à l'intérieur du récipient.68. Assembly according to any one of claims 62 to 66 characterized in that the composition is substantially at atmospheric pressure inside the container.
69. Procédé cosmétique de maquillage ou de soin non thérapeutique des matières kératiniques, en particulier de la peau ou des lèvres, comprenant l'application sur les matières kératiniques, en particulier de la peau ou des lèvres, d'une composition selon l'une quelconque des revendications 1 à 61.69. Cosmetic process for making up or non-therapeutic care of keratin materials, in particular of the skin or the lips, comprising the application to the keratin materials, in particular of the skin or the lips, of a composition according to one any of claims 1 to 61.
70. Procédé cosmétique de maquillage ou de soin non thérapeutique des fibres kératiniques, en particulier des cils comprenant l'application sur les fibres kératiniques, en particulier les cils, d'une composition selon l'une quelconque des revendications 1 à 61.70. Cosmetic process for making up or non-therapeutic care of keratin fibers, in particular the eyelashes, comprising the application to the keratin fibers, in particular the eyelashes, of a composition according to any one of claims 1 to 61.
71. Utilisation d'une composition selon l'une quelconque des revendications 1 à 61 , pour obtenir un dépôt, notamment un maquillage, non transfert sur les matières kératiniques, en particulier sur la peau, les lèvres ou les fibres kératiniques. 71. Use of a composition according to any one of claims 1 to 61, to obtain a deposit, in particular a make-up, non-transfer on keratin materials, in particular on the skin, lips or keratin fibers.
PCT/FR2003/003714 2002-12-12 2003-12-12 Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase WO2004055082A2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2004559837A JP4167229B2 (en) 2002-12-12 2003-12-12 Transfer-resistant cosmetic composition comprising a non-silicone grafted ethylenic polymer particle dispersion in a liquid fatty phase
ES03813190.0T ES2627551T3 (en) 2002-12-12 2003-12-12 Non-transfer cosmetic composition comprising a dispersion of particles of a non-siliconized grafted ethylenic polymer in a liquid fatty phase
US10/538,783 US7794695B2 (en) 2002-12-12 2003-12-12 Non-transfer cosmetic composition comprising a dispersion of particles of a silicon-free grafted ethylene polymer in a liquid fatty phase
AU2003300602A AU2003300602A1 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase
EP03813190.0A EP1572137B1 (en) 2002-12-12 2003-12-12 Non-transfer cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase
FR0450540A FR2863493B1 (en) 2003-12-12 2004-03-18 COMPOSITION COMPRISING A PARTICLE DISPERSION OF A GRAFTED ETHYLENE POLYMER AND A FILMOGENIC AGENT
PCT/IB2004/004127 WO2005058274A1 (en) 2003-12-12 2004-12-10 Composition comprising a dispersion of particles of a grafted ethylenic polymer and a film-forming agent

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FR0215737A FR2848558B1 (en) 2002-12-12 2002-12-12 ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION
FR02/15738 2002-12-12
FR02/12737 2002-12-12
FR0215739A FR2848560B1 (en) 2002-12-12 2002-12-12 ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION
FR02/15739 2002-12-12
FR0215738A FR2848559B1 (en) 2002-12-12 2002-12-12 ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS AND NON - SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION

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PCT/FR2003/003714 WO2004055082A2 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase
PCT/FR2003/003712 WO2004055080A2 (en) 2002-12-12 2003-12-12 Composition comprising a dispersion of particles of a grafted ethylene polymer and a gelling agent
PCT/FR2003/003707 WO2004055077A2 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer
PCT/FR2003/003709 WO2004055078A1 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer and a non-volatile oil
PCT/FR2003/003711 WO2004055074A2 (en) 2002-12-12 2003-12-12 Long-lasting lipstick comprising a dispersion of a grafted ethylene polymer
PCT/FR2003/003710 WO2004055079A2 (en) 2002-12-12 2003-12-12 Non-transfer cosmetic composition comprising a dispersion of a grafted ethylene polymer
PCT/FR2003/003708 WO2004055073A2 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer
PCT/FR2003/003713 WO2004055081A2 (en) 2002-12-12 2003-12-12 Composition for coating keratin fibres, comprising a dispersion of polymer particles

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PCT/FR2003/003707 WO2004055077A2 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer
PCT/FR2003/003709 WO2004055078A1 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer and a non-volatile oil
PCT/FR2003/003711 WO2004055074A2 (en) 2002-12-12 2003-12-12 Long-lasting lipstick comprising a dispersion of a grafted ethylene polymer
PCT/FR2003/003710 WO2004055079A2 (en) 2002-12-12 2003-12-12 Non-transfer cosmetic composition comprising a dispersion of a grafted ethylene polymer
PCT/FR2003/003708 WO2004055073A2 (en) 2002-12-12 2003-12-12 Cosmetic composition comprising a polymer
PCT/FR2003/003713 WO2004055081A2 (en) 2002-12-12 2003-12-12 Composition for coating keratin fibres, comprising a dispersion of polymer particles

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EP (4) EP1572770A2 (en)
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